text:
How to Blog a Book
Write, Publish, and Promote Your Work One Post at a Time
(If any tax is payable it will be calculated and shown at checkout.)
Preview (read now) Add to my own site Give this ebook to a friend Add to my wishlist Author's page Publisher's page
How to Blog a Book teaches you how to create a blog book with a well-honed and uniquely angled subject and targeted posts?and how to build the audience necessary to convince agents and publishers to make your blog into a book.
Inside you'll find:
- Basic information on how to set up your blog and the essential plug-ins and other options necessary to get the most out of each post
- Steps for writing a book easily from scratch using blog posts
- Advice on how to write blog posts
- Tips on gaining visibility and promoting your work both online and off
- Tools for driving traffic to your blog
- Information on how to monetize an existing blog into a book or other types of products
- Profiles with authors who received blog-to-book deals
F+W Media; April 2012
168 pages; ISBN 9781599635422
Read online, or download in secure EPUB
Title: How to Blog a Book
Author: Nina Amir
168 pages; ISBN 9781599635422
Read online, or download in secure EPUB
Title: How to Blog a Book
Author: Nina Amir
Buy, download and read How to Blog a Book (eBook) by Nina Amir today!
More Language Arts
The Study of Language 2014 US$ 26.00 336 pages
A Rulebook for Arguments 2008 US$ 8.95 105 pages
Woe Is I 2010 US$ 12.99 288 pages
Explicit Direct Instruction for English Learners 2012 US$ 36.95 344 pages
Subject categories


text:
(й»'и±љгЃ—г'ѓгЃ¶гѓ»ж—¬е'ЊйЈџ з"Ўй–Ђж–°е®ї)
Enjoy a relaxing meal of seasonal flavors amid soft jazz music in our modern dining parlor. Try our black pork Shabu-shabu. We offer value plans with unlimited drinks for parties. Private dining rooms available.
Step out of the clamor of Shinjuku into dry landscape gardens and wooden surroundings. Relax amid the wildlife illustrations from Japanese traditional scrawls that adorn our walls. Enjoy a meal for 2 in a private room, or dine in our traditional seats. Treat yourself to our signature dish, collagen-rich Kagoshima Black Pork Shabu-shabu. It's delicious with Japanese broth and Yuzu-fruit pepper. Finish with Okinawan soba noodles added to the last of the broth for flavor that can't be beat. We offer many other Japanese dishes as well, all at reasonable prices. We're a great place to entertain visitors or to host a banquet.
other photos
Restaurants in the neighborhood
Sightseeing spots in the neighborhood

subset: commoncrawl


text:
I have a computer with an integrated gpu on the motherboard. Because I wanted to use two monitors and my motherboard only has one VGA port, I bought an ATI radeon HD 6450. Both my monitors have a VGA connector, so I also bought an adapter (VGA to DVI). The VGA port on the card works fine, but I can't get the DVI port to work. Does anybody know how I can get this to work?
Take the 2-minute tour ×
Super User is a question and answer site for computer enthusiasts and power users. It's 100% free, no registration required.
Try to obtain latest Catalyst drivers and try to detect second monitor(enable) in Display options (AMD/ATI) Display Manager, and also you need check is there any conflicts in BIOS with integrated graphics like Josh already proposed. Also in every manual that comes with Graphic cards is explained a way to connect cabling to multiple displays. Maybe Yours problem is in DVI/VGA adaptor and/or cabling.


text:
Best Buy Fashion #9154
Release Date: 1/1/1976
Product Code: 9154
Barbie® doll's patriotic set featured white slacks stitched in red with elasticized waist and a red tricot tee shirt with flag decal.
All images and descriptions courtesy of Collector Books, publisher of "Barbie® Doll Fashion: Volume 3" by Sarah Sink Eames.
Production doll may vary from the photo shown above. Mattel reserves the right to modify the fashion/fabrics, sculpt, hair color/style, and accessories. Doll cannot stand alone as shown.
Collector Photos
No one has uploaded any photos.


text:
The past few weeks have been insanity for me! I've been crazy busy with work, helping plan for our school festival and working on lesson plans, plus working on my online classes. I've also been really busy trying to stay outside of my apartment before winter really hits. I know once it gets really cold my ass won't be going anywhere. I've been going on hikes/walks around Johnny's neighborhood, visiting tons of cafes and new restaurants, watching my students play soccer games after school, and taking in the gorgeous fall colors and scenery.
As I said earlier, my school festival was last week, and it was TONS of fun. The first day was sports day. Each class dressed up in costumes or matching outfits and competed in various outdoor activities. Moms came and provided snacks and hot food for all the students to purchase. I've never seen them so excited!
On the second day, the whole school was transformed into one giant marketplace. Each class was in charge of creating and managing their own business. Most classes had cafes where they served coffee, tea, waffles, pancakes, and other sweets. But some classes went above and beyond and created nightclubs, complete with DJs, bartenders and strobe lights, PC bangs, nail and hair salons, Korean BBQ restaurants… the works. My students are so incredibly talented and creative! I'm currently working on editing a video to show to them…and to you!
If you live in Bundang/Yongin, please make your way to Pizzeria Da MOON in Jukjeon cafe street. I've been about 6 times in the past 3 weeks. I'm obsessed.
11 Comments on October Lovin'
I recognize that beer tower…
The pizza looks amazing! Looks like you are really enjoying teaching, can't wait to start myself!
I'm glad you're still exploring! 😉 I've already gone into hibernation mode.
Allergic to rice? What a nightmare. Fabulous photos (as always) x
Whenever I feel like teaching kids/teens would be a nightmare, I look at your posts and photos and think, 'Wow. It would be a *different* kind of challenge but these kids are incredible.' What a great way to spend the Autumn.
You're gorgeous!!! I love how you seem so close and comfortable with your students! I want to work and live in Korea too T_T Might I ask what camera and lenses you use? You're pictures look so crisp! Do you do edit/enhance them or anything? What filters do you use?? Please help a photography-beginner such as myself Please email me back


text:
Liz Johnson, Ollie and Sam Hynd, Hannah Russell and Louise Watkin go for swimming gold at Aquatics Centre tonight
No Ellie Simmonds, no problem. If the 17-year-old has dominated the Aquatics Centre for much of this week, today promises to be the day when the rest of Great Britain's swimmers step out from her shadow. This evening brings two finals to savour, and realistic hope of four more gold medals to add to the host nation's gilded tally.
The most mouth-watering clash comes in the women's 100 metres breaststroke in the SB6 category, where Liz Johnson, the reigning champion, won her heat, breaking the Paralympic record in a time of one minute 41.09 seconds and looking thoroughly indomitable. A


text:
SUMMERVILLE -- If her Brownsville neighbors want to march in the street in protest of the Confederate battle flag outside her home, Annie Chambers Caddell doesn't mind.
"I think I'll join them. I think I'll protest the fact that they're protesting over nothing," she said, adding that she might bring along her pet python.
Caddell is the new resident who has outraged neighbors in the historically black community in Summerville by flying the flag from her porch alongside an American flag.
She doesn't understand the hostility, she said Thursday. But no, she won't back down. Not only will the flag stay up, she's having battle flag drapes made for the window. The Confederate motif is part of who she is, she said: a daughter of the South.
"I don't understand their concerns," she said. "If they said I was racist, that I was abusing them, I would be very concerned. But's that's not the issue."
People who live in the neighborhood said they understand that some people consider it heritage, but to them the connection is to slavery, lynchings and the Ku Klux Klan.
They are planning a protest march and will petition Town Council on the matter at its Oct. 13 meeting.
"This is the first time we've ever had anything like this in our community. We have always gotten along. This is a slap in the face," said Alfreda Brown, a member of the community's District 1 Civic Association and wife of Town Councilman Aaron Brown.
Caddell, 50, has suffered from Crohn's disease for 26 years, she said. Crohn's is a chronic disease, and her prognosis is poor, she said. She is on disability.
And the neighbors' dispute over the flag has erupted into a media event. Dozens of people drive past the house each day to get a look.
Caddell talked with The Post and Courier at a table under the tree in her front yard, sitting with a pack of cigarettes and an orange Clemson Tigers mug. She wore peace symbol earrings to make a statement, she said.
A neighbor rode by on a bike and they exchanged waves and hellos. People yelled something that couldn't be made out from two cars that passed by. Otherwise, the neighborhood was quiet.
Caddell has been married and divorced seven times. Born and raised in Charleston and Goose Creek, she moved away for 10 years to Georgia and then to Ohio.
She moved back to South Carolina to be closer to family. She wanted to buy her old family home in Goose Creek, but another bid took it. She looked at the cedar, block and brick Brownsville house and wanted it right away.
She made eight visits to the neighborhood before moving but didn't realize that most of the neighbors are black.
"Did I check out this neighborhood? No. Does it bother me? No," she said. She has put up the Confederate memorabilia wherever she has gone, she said, and has never had a problem before.
Her neighbors have been good to her, she said, helping her as she settled. The battle flag and decorations didn't come out for a month.
"It's a flag. It's my heritage. I tell you from the bottom of my heart I did not intend for this to bother anybody," she said, placing a hand over her heart.
"It's not like I'm wrapping myself up in it and walking down the street."
Reach Bo Petersen at 937-5744.
- Keywords
Notice about comments:
The Post and Courier is pleased to offer readers the enhanced ability to comment on stories. Some of the comments may be reprinted elsewhere in the site or in the newspaper. We ask that you refrain from profanity, hate speech, personal comments and remarks that are off point.
We do not edit user submitted statements and we cannot promise that readers will not occasionally find offensive or inaccurate comments posted in the comments area. If you find a comment that is objectionable, please click the X that appears in the upper right corner when you hover over a comment. This will send the comment to Facebook for review. Please be reminded, however, that in accordance with our Terms of Use and federal law, we are under no obligation to remove any third party comments posted on our website. Read our full terms and conditions.


text:
pilpel dips review
I was recently introduced to pilpel dips during our Melbourne Cup lunch at work. Having coeliac and gluten and dairy intolerant employees always makes these kind of work functions a challenge, however we always manage to have an amazing spread of food. Our Melbourne Cup lunch was no different with bread (gluten free and glutenous), crackers, antipasto items including sundried tomatoes, ham, salami and olives, prawns and a selection of pilpel dips.
pilpel dips are all gluten and dairy free simply because the chef believes that you shouldn't add anything to food that's not essential to the flavour. At our lunch we had the hummous, beetroot almond and baba hummous dips. All of the dips were fantastic however my favourites were the baba hummous and beetroot almond. The baba hummous dip is smoked eggplant with creamy hummous and considering I love anything eggplant it was bound to be a winner. It was full of flavour and was good enough to eat on a plain cracker or piece of bread with nothing else (e.g. cheese or sundried tomatoes) needed. I actually preferred having the dip just with a plain cracker so that you could experience the full flavour of the dip. The beetroot almond dip has a tang to it and at first I couldn't work out what this was, but after reading the ingredients I recognised the hot english mustard flavour. This is a great variation on the traditional beetroot dip. The hummous was also very good, quite different from other hummous' I have tried as it was very smooth and creamy.
We purchased the dips at the Chatswood Chase Coles but if you want to know where to buy them in your area you can find out here.
What is your favourite dip flavour and brand?
|Print article
|This entry was posted by Petra on November 4, 2010 at 8:46 am, and is filed under Dairy free, Gluten Free Product Reviews, Reviews. Follow any responses to this post through RSS 2.0. You can leave a response or trackback from your own site.
You must be logged in to post a comment.
No trackbacks yet.
Swissotel Amsterdam, Dam Plaza Restaurant
about 9 months ago - Comments Off on Swissotel Amsterdam, Dam Plaza Restaurant
Working in hospitality definitely has its perks and a stay at the Swissotel in Amsterdam on staff rates was one that I took up recently. When I made the reservation I made a note that I was gluten free, just in case they wanted to leave me a small arrival treat When we checked into…
Ruby's of London
about 9 months ago - Comments Off on Ruby's of London
It's nice to see gluten free cakes, cupcakes and doughnuts popping up everywhere these days. Not that I eat them often, but it's nice to have the choice of having a sweet treat along with your tea or coffee. I have stumbled across Ruby's of London a couple of times now, at the market in…
Bread Steet Kitchen, London
about 9 months ago - No comments
If you haven't eaten at Bread Street Kitchen yet, Gordon Ramsay's restaurant at One New Change near St Paul's, I highly recommend you do! After asking for gluten free options I was presented with a gluten free menu which contained most of the items from the regular menu. I was also presented with gluten free…
Gluten-Free Chicken from Leon
about 9 months ago - No comments
I have posted about Leon before, about how I not only love their food but how they cater for so many dietary needs including gluten free. Last week I was lucky enough to try their new menu item, Gluten-Free Chicken along with a couple of other goodies. When trialling gluten free products I always like…
Señora Rosa, Eindhoven, Netherlands
about 11 months ago - No comments
If you're looking for a gluten free meal in Eindhoven I highly suggest you check out Señora Rosa. It is a Spanish restaurant and tapas bar and not only are the staff highly knowledgeable of what is gluten free, the food is amazing. We were all so hungry when we arrived that I completely forgot…
The Real Greek, London
about 1 year ago - No comments
One day last summer a friend and I were walking along the Thames soaking up the sunshine looking for a place to have lunch. Whilst walking past The Real Greek we noticed a lunch deal that looked too good to miss. I can't remember exactly what it was but it was similar to the current…
Cauliflower Gratin
about 1 year ago - No comments
Looking for a gluten free alternative to couscous, or just a change from rice and quinoa? I got this recipe from Jamie's 15 minute meals and I absolutely love it. All you need to do is chop up half a cauliflower head and pulse in a food processor until finely blended. Place in a bowl…
Leon Healthy Fast Food
about 1 year ago - No comments
Leon is an awesome restaurant if you are looking for healthy, reasonably priced food on the go. Oh and they label all of their menu items as to whether they are gluten free, wheat free, daily free, low Glycemic load, low in saturated fat, vegetarian, vegan, nut free and treat foods so pretty much all…
Vozars, Brixton Village
about 1 year ago - No comments
I was very excited to be invited to a Gluten Free Tweet Up over the weekend at Vozars, a gluten free cafe, deli & restaurant in Brixton Village. What is a Gluten Free Tweet Up I hear you asking? Well basically those who are gluten free and who are on Twitter, get together for a…
A gluten free Christmas
about 1 year ago - No comments
This is just a short post for all of those in London who are looking to make a gluten free Christmas Day meal. I was pleasantly suprised to find products, in particular, gravy and custard, naturally gluten free as opposed to getting them from the free from isle (which actually didn't have any gravy or…


text:
Soften ecstasy law, say police chiefsSenior police officers have called for ecstasy to be treated as less dangerous than heroin or cocaine, just days after the Government ordered a relaxation of the cannabis laws.
Front page
UK student's 'key terror role'FBI suspects Birmingham man helped rent San Diego apartment used as a base by hijackers who crashed into Pentagon.
News p4
One is in the moneyPrince Charles is aiming to double his annual income to over £14 million. A blueprint drawn up for the Duchy of Cornwall, the Prince's private estate, will make him one of Britain's biggest charitable benefactors if it succeeds.
News p5
In briefHunt for hit-and-run men who pulled victim from under van | Barrymore in Bashir interview | Whisky sales boom in Asia | Arrests over dead journalist
Concorde makeover 'puts glamour back in flight'It was a futuristic dream - the world's safest and most stylish plane. But when it crashed near Paris last year, killing 113 people, critics said Concorde would never fly again. Now the pride of British Airways is back.
News p7
But there's only one problem. I hate dopeEuan Ferguson went out yesterday to test the new liberal attitude to cannabis. Buying it was easy, but smoking it made him sick.
FO tried to ban Brecht from BritainMinisters tried to stop the East German playwright Bertolt Brecht and his Berlin theatre group coming to London during the Cold War, according to newly declassified records.
News p8
Net shopping hooks army of addictsThe addictive pull of internet shopping is dragging thousands of victims into a spiral of debt, including thousands of women who have run up huge credit card bills they cannot repay.
Girls 'held back by stereotypes'Sexist stereotyping is so ingrained in young children that Britain is in danger of entering a new era of sex discrimination in work, pay and public life.
Christie was film pioneerA British Museum curator has discovered a reel of film shot by Agatha Christie that inspired the author to write some of her most famous detective novels, including Death on the Nile.
News p9
Airlines in court over blood clotsThe crisis facing British Airways and Sir Richard Branson's Virgin Atlantic will intensify tomorrow, with the start of a High Court row over claims that they refused to warn passengers of the dangers of 'economy class syndrome'.
Test case could set Hindley freeA case that could lead to freedom for some of Britain's most notorious killers including Moors murderer Myra Hindley will begin at the Court of Appeal this week.
News p12
Sports coaches 'abusing children'Sports bodies face allegations that hundreds of young athletes have been subjected to bullying, verbal assaults and sexual abuse by coaches who were meant to groom them for stardom.
Tourists turn a blind eye to rights abuses
Shame of Brits abroad: British put holiday bargains before ethical worries.
News p13
Charities fear backlashover sitcom's Mr NastyIt is a cutthroat business, dominated by attention-seeking inadequates and fraudulent do-gooders. Welcome to the world of the British charity shop - as portrayed by Mr Charity, the BBC's latest sitcom star.


text:
Top Celebrities-Caught-Cheating Scandals Have you noticed that the gossip mill has been full of celebrities-caught-cheating stories of late, of varying degrees of veracity? There's Patrick Schwarzenegger's purportedly cheating on Miley Cyrus and vice versa. Chris Martin's perhaps cheating …Read more. Ask Stacy -- Week of 6/27/15 DEAR STACY: What is Tracey Ullman up to? — Leon D., Newark, New Jersey DEAR LEON: It has been a time of upheaval for the comedy star, whose husband, producer Allan McKeown, died of prostate cancer at age 67 on Christmas Eve of 2013, and whose …Read more. Hollywood in Its Glory Alive Again in 'Starflacker' Kirk Douglas and John Wayne, conspiring to make the most of a so-called "feud" between them in order to grab the attention of the press and public — just as their "The War Wagon" movie was hitting theaters. Doris Day, generously and graciously …Read more. Ask Stacy -- Week of 6/20/15 DEAR STACY: I like the actor who plays Chet in "UnREAL," Craig Bierko. I know I've seen him a lot of times before. Can you give some background? There is a cloud of secrecy as to his personal life, it seems. — VBLana DEAR VBLANA: The 50-year-…Read more.more articles
Blue Collar Comedy Reunion Tour a Maybe, Says Engvall/Arnold and Maria's Election Night
Attention, Blue Collar Comedy fans. Bill Engvall tells us there's a possibility of a Blue Collar Comedy reunion tour.
"Would I love to do a reunion tour? Yeah. Maybe do 10 or 12 cities in one year. I don't think I see it going any further than that, though," claims the comedian, who is the creator and star of "The Bill Engvall Show" on TBS.
"If there is a 'Blue Collar' thing, it will be a lot easier to go back and do that now that I've done my own thing." Referring to the successes of cohorts Jeff Foxworthy and Larry the Cable Guy, he adds candidly, "Everybody else had done stuff. I had done stuff but nothing on my own. Being a part of 'Blue Collar' was like being married to a rich girl. It's great for a while, but then you want to be able to make your own living. This was the first project that I had done outside of the guys, so I'm thrilled that it's going into its third season."
We caught up with Engvall and his co-star Nancy Travis, who are anticipating the Nov. 15 finale of their second season, when they will debut two new episodes.
"I think the first year we were searching for the target, and this year we hit it. We located what the show is, and that kind of took off," says Travis, who plays Bill's wife Susan. "The thing with cable is you only get to do a dozen episodes. By the time you finish those you're ready to do another 12."
One of the episodes has a Christmas theme. "We shot it in June, when it was like 105 degrees," recalls Travis. "We're like, 'How do we get into the spirit of that?'"
"You ain't kidding!" adds Bill with a laugh.
TWO PARTIES, TWO PARTIES: California's First Couple continues to bewilder friends and fans. Staunch Democrat Maria Shriver was by her hubby, Republican Gov. Arnold Schwarzenegger's side for his election night party at the Beverly Hilton Hotel this week. But not the whole party. Via sources there, we hear she "left early and went to an Irish party. And when she came back, she was very happy."
ALSO: We get word that the crew for Julie Taymor's "The Tempest" came up with a new word Tuesday night. They are on location in Hawaii, President-elect Obama's home state, filming the Shakespeare redux under Taymore's innovative hand, (starring Helen Mirren, Jeremy Irons, Djimon Hounsou, Russell Brand, Alfred Molina and Geoffrey Rush).
LOOK OUT BELOW: Jason Gedrick is just back to the States after a month in Romania for the international production of "Sand Serpents," a Sci Fi Channel movie in which soldiers in Afghanistan encounter carnivorous subterranean creatures awakened by the fighting above ground. Director Jeff Renfroe's recent comment that the scenario "demands that we tread cautiously and responsibly through the thematic elements of the U.S. presence and actions in the Middle East" hints that the movie has a real-life political overlay. Not to the actors, to hear Gedrick tell it.
"That was definitely a question I asked from the get-go," he says. "I wanted to know how much metaphor plays into a show like this. The answer was, none. This is a fantastical situation. It's more about survival. Whatever conclusions people want to make about surreptitious events happening in the world — whether it be violence or acts of vengeance — whatever conclusions they draw, it's just coincidental."
As far as working on the movie, says Gedrick, "So much of it is just glorified childhood, really. You dress up in Army gear and play army games. You shoot real weapons with blank charges — but they're real weapons. One of the reasons you do it is, you're going to have fun." He adds, "We had an incredible English and Canadian cast, and a terrific international crew. The talent overfloweth on this project, and because of that, a couple million dollar budget will look like double that, if not more."
WOMAN OF ACTION: "Chuck" leading lady Yvonne Strahovski reports, "I'm getting to do physical stuff in every episode" of late — and she couldn't be happier about all that action. "We've been doing more of the wire stunts, which is really fun," says the Maroubra, Australia-born 26-year-old who loves rock climbing and hiking when she's not working. Her dance training helps in the fight scenes and other choreographed action, she says. "From age 5 to 18 I was in dance, but that kind of stopped when I went into drama school."
With reports by Emily Feimster.
To find out more about Marilyn Beck and Stacy Jenel Smith and read their past columns, visit the Creators Syndicate Web page at www.creators.com.


text:
Sherried Almond Torte
|4 , separated
|All purpose flour
|1 Cup (16 tbs)
|Baking powder
|1 Teaspoon
|1⁄4 Teaspoon
|1⁄3 Cup (5.33 tbs), cooled
|Vanilla extract
|1 Teaspoon
|Almond extract
|1⁄2 Teaspoon
|2 Cup (32 tbs)
|2 Cup (32 tbs)
|1⁄2 Cup (8 tbs)
|Toasted slivered almonds
|3⁄4 Cup (12 tbs)
Beat egg whites until foamy; gradually add 4 tablespoons of the sugar and continue beating until soft peaks form.
Beat egg yolks with remaining 4 tablespoons of sugar.
Gradually fold beaten yolks into beaten whites.
Sift flour, baking powder, and salt together.
Sprinkle over egg mixture about 1/4 cup at a time and fold in gently.
Fold in butter, vanilla extract, and almond extract (if used).
Pour into a greased 9 inch square baking pan.
Bake at 375°F about 30 minutes, or until golden brown.
Remove from oven and pierce all over with a long handled kitchen fork or ice pick, making holes through to bottom.
Meanwhile, prepare sauce.
Combine sugar and water in a saucepan and boil over low heat, stirring occasionally, to soft ball stage (234°F).
Stir in sherry.
Pour hot sauce over hot cake, sprinkling entire top with almonds as last third of sauce is poured over top.
Let stand in baking pan until thoroughly cooled.
Serve from pan, or remove to a serving plate.


text:
Originally written on Fox Sports North | Last updated 3/18/12
On Sunday, mid-March seemed a lot like early January. Darko Milicic started, and Anthony Randolph played rather than sat out as a healthy scratch. There were 21 Minnesota turnovers -- far too many -- and the Kings scored 29 points off of them en route to a 115-99 blowout. Sounds a lot like the Timberwolves of two months ago, no? Some things have stayed constant this season. Milicic played just six minutes, scoring two points in yet another disappointing performance. Kevin Love finished with another double-double, 21 points and 11 rebounds. Luke Ridnour was just fine, with 13 points and five rebounds. But disappointing, a double-double and just fine weren't enough on Sunday. It's the variables that reveal the truth, that injuries and lapses tripped up this once-promising squad in its 46th game. If it were January, Michael Beasley would be injured. Derrick Williams wouldn't have logged 33 minutes and scored 16 points; his development has become a bright spot only in the season's se...
Comments are closed.
What do you think?To leave a comment, you can:
NBA News
Delivered to your inbox
You'll also receive Yardbarker's daily Top 10, featuring the best sports stories from around the web. Customize your newsletter to get articles on your favorite sports and teams. And the best part? It's free!
Follow us on Twitter
|Best of Yardbarker
|NFL News
|MLB News
Today's Best Stuff
For Bloggers
Join the Yardbarker Network for more promotion, traffic, and money.
Company Info
What is Yardbarker?
Yardbarker is the largest network of sports blogs and pro athlete blogs on the web. This site is the hub of the Yardbarker Network, where our editors and algorithms curate the best sports content from our network and beyond.
|© 2015 Yardbarker, Inc. All rights reserved. Use of this website (including any and all parts and components) constitutes your acceptance of these Terms of Use and Privacy Policy. (What's New?)


text:
Results: 1 - 4 of 4
My Usual Game
This is the best sunscreen for golfers, and I'm not kidding
As I drove home from my dermatologist's office, I felt more than slightly annoyed. Slicing two bumps from the side of my nose had taken the doctor roughly eleven seconds, from Novocain to Band-Aid, yet...
Saturday, 11/15/2014 at 11:29AM
- keywords:
- David Owen,
- basal cell carcinoma,
- melanoma,
- skin cancer,
- sunscreen
Health & Fitness
Fitness Friday: Hey, you, don't forget the sunscreen
Editor's note: Every week my colleague Ron Kaspriske, Golf Digest Fitness Editor, presents Fitness Friday on the Instruction Blog. This week he talks about how to avoid sun damage and skin cancer. Look for Saturday...
Friday, 7/29/2011 at 1:00AM
- keywords:
- Dr. Michael Kaminer,
- Fitness Friday,
- Ron Kaspriske,
- melanoma
Magazines / The Digest | Summer Golf
Safe Sun
Arm yourself in the battle against skin cancer: Dr. Michael Kaminer, a dermatologist, avid golfer and regular contributor to Golf Digest, debunks some myths about protecting yourself from skin cancer and other sun-related damage.
August 2011
- keywords:
- health,
- sunscreen,
- sun protection,
- Dr. Michael Kaminer
Magazines / Health
Five Questions About Skin Cancer
We get answers from two dermatologists about how to protect yourself.
March 2011
- keywords:
- Skin Cancer,
- Ian Poulter,
- Rory Sabbatini,
- Bill Murray,
- Anna Rawson
Results: 1 - 4 of 4


text:
Catalogue Number: 239-0392
Sorry, there are currently no sellers for this product.
Product Details
Raffia is a 100% natural product which is obtained from the fronds of the raffia palm in Madagascar. The raffia palm regenerates itself and is environmentally friendly. Used for: handicrafts, gift wrap, packaging and pot pourri
Product specifications
Product specifications
Key Information
|Basketry & cane work


text:
U.S (PRWEB) May 20, 2013
Laptop radiation shield leader, DefenderPad, announced today that it is now not only a hit in the U.S., but has a growing demand in international markets according to representatives for the company.
"With international sales continuing to expand, we're now actively seeking out regional wholesaler and distribution channels to better service the world markets," a spokesman for DefenderPad said.
DefenderPad, which according to an independent study, is the only laptop radiation shield that blocks virtually all harmful radiation, its spokesman explained, has begun negotiating agreements with potential distribution partners in European countries.
"We are expanding into international markets," the spokesman pointed out, before adding, "DefenderPad is searching for world partners that are best in class channels at delivering the highest quality of products at the best prices."
Plans include having partners offering product information tailored to local markets. Sales and support collateral as well as websites, the spokesman stressed, will be in the native language of the countries served.
"Customer experiences will be improved with product delivery times reduced from two to three weeks to two to three days," the spokesman said.
DefenderPad is a unique and pioneering solution that provides ultimate safety while using today's modern mobile technology.
DefenderPad blocks nearly 100 percent of all potentially harmful Electromagnetic Radiation (EMR) and greatly reduces heat emitted by laptops, tablets and other electronic devices.
In fact, an independent FCC certified lab test revealed The DefenderPad is the only product capable of fundamentally eliminat
|Source: PRWeb
Copyright©2012 Vocus, Inc.
All rights reserved


text:
How can I generate and install documentation for all locally installed cabal packages? I turned on the documentation flag in ~/.cabal/config which means that all newly installed packages will have documentation also generated. But how to generate documentation for all already installed packages?
Is there a way to automatically
cabal install --reinstall all already installed packages? And more importantly, is that a good idea?


text:
From the article: Flu Shots and Pregnancy:
Flu and pregnancy don't mix well. Getting the flu is more dangerous for pregnant women than when you aren't pregnant. The flu shot is considered by physicians to be the easiest way to prevent the flu. But some women are worried about miscarriage or of the flu shot causing the flu. What are your concerns about the flu shot in pregnancy? What does your doctor or midwife recommend? Do they ever recommend that a flu shot not be given? Have you had one? What happened? Will you do it again?
I took a flu shot during pregnancy
- It seemed to me that the risk of the flu shot was absolutely minimal compared to the risk of getting the flu while pregnant. So I didn't hesitate about taking the flu vaccine.
- —Guest Sandra
I worried, but did it.
- I was really worried about it. My doctor gave me all the inserts and told me to go home and read them and to look online. It was great that he respected that I was worried. So in the end it was the right decision for me. My doctor said he wouldn't push it. It was only a mildly uncomfortable shot but it's been two weeks and I'm not sick, so I think I've escaped unscathed from the actual vaccine.
- —Guest Mandy


text:
I think I got a little carried away talking about the SC command line tool last week and how to use it to help manage drivers. So carried away in fact, that I forgot to explain how to install a new driver.
For hardware that has an in the box driver in Longhorn Server, you just need to install the hardware, startup the server, and log on to the box. Plug and Play will detect the hardware change, rescan, and automatically install the driver. There is no UI or need for administrator interaction. In the case of a new network adapter, running IPconfig will show the new adapter and its IP address (if you are using DHCP). You can also use SC.exe to see that it was installed, but I told myself no rambling about SC.exe this week, so you'll have to look at last weeks post for the details on using it.
For hardware that does not have a driver included in Longhorn Server, such as a new piece of hardware that comes out after release, as long as you have a PnP driver for it, it can be installed from the command line. To do this, you need to either copy the driver files to a temporary folder on the Server Core box or make them available on a network share. In Server Core beta 2, you then run the Drvload.exe command to install them, pointing the tool at the driver inf file:
Drvload <path>\<driver>.inf
Drvload <path>\<driver>.inf
This will install the driver in the repository and kick off a PnP rescan, which will detect the hardware, find the new driver, and install it for you.
Hopefully this fills in the gap in the hardware story that I left last week.
Thanks for the syntax. That'll help my implementation - trying to think "core" is interesting at best, but I think the end product will be worth it.
One important thing to mention is that the drivers have to be signed! If they are not you'll get an error...
I received the following error:
"Drvload: Unable to load <correct drive path to driver.inf> (Error 0xe000023f)."
Any thoughts? These VMware drivers might not be signed.
Yes, I forgot to mention that, in beta 2 the drviers do need to be signed. We are looking into a solution for that for beta 3.
I haven't seen that error before, when you install the drivers in a regular install do you get prompted that the drivers aren't signed?
Yes. In regular Longhorn, it does warn about being an unsigned driver, so I will have to wait until beta 3 before loading customized drivers. I am sure the platform (VMware VM) is probably not on the HCL.
I am not sure what drivers cnschindler was trying to install. But I am in the process of setting up LH Server Core Beta 2(build 5384) on Vmware Server 1.0 (Build 28343). Installed core and as I guessed there were no drivers. No experimental support for LH from Vmware yet in the free server product, but managed to get the NIC drivers from http://www.amd.com/us-en/assets/content_type/utilities/V4.51.zip as per a VMware forum post and all is well so far.
Just wanted to say the vista experimental support works fine in LH. Please ignore comment of "no experimental support".
Sorry the VMware driver issue seemed to be bowulf's issue no cnschinder. Sorry about that too ;-0


text:
the 770 is a relabeled 710, and it has had problems. I would stay away from this model. I have had problems with mine.
Results 21 to 40 of 41
Remove Ads
Search tags for this page
.30x06 reloading,
270 winchester vs 30x06,
30x06 rifle,
30x06 rifle model 700 sprg,
30x06 rifle model 700 sprg value,
higher caliber .308 winchester or 30x06,
how good is a 30x06 rifle,
hurter rifle 308,
opinons about the remington model 770 in .270win w/scope,
remington 700 30x06,
ruger 30x06
Click on a term to search for related topics.


text:
The Manchester Monarchs, AHL affiliate of the Los Angeles Kings, made a roaring comeback to defeat the Hershey Bears after having a 3-0 deficit Saturday night.
The Manchester Monarchs started the important game riding on a 3-game losing streak while the Hershey Bears, AHL affiliate of the Washington Capitals, have lost 3 of their last 5 games. Both teams needed the points as Hershey dropped to 8th in the Eastern Conference for the Calder Cup Playoffs after their 3-2 SO loss Friday night against a strong Connecticut Whale team. Bears head coach, Mark French, decided to put Philipp Grubauer in while opposing Monarchs coach, Mark Morris, put Martin Jones in for the second straight game. Once the puck dropped the Monarchs controlled the first half of the period until Monarchs center Linden Vey, who is 3rd in the league for assists, went to the box for hooking at 9:21 of the first period. The monarchs did hit the both cross bars on the goal but didn't go in after further review. Once Hershey got there extra man on the ice they were piling shot on Jones left and right but couldn't capitalize on their power play. Then at 15:50 of the first period Monarchs defenseman, Andrew Bodnarchuk, went off for cross-checking, Hershey soon got on the board with a tip-in from Bears center, Ryan Potulny, past Jones at 16:17 of the first. The Bears would tack on another goal with just 9 seconds to go in the period by Bears' Boyd Kane. Kane reached a milestone by scoring giving him his 500th career point in the American Hockey League. At the end of the first Hershey led the shot total with 11 while the Monarchs only had 7.
When second period started the Monarchs were showing strength keeping the puck in there zone the most of the period. Potulny collected another goal and 4:13 of the first period to beat Jones with a wide open left side. The Monarchs comeback started at 6:16 of the second period when Monarchs center Andy Andreoff got his 10th of the year with a turnaround shot from the bottom of the circle to beat Grubauer. The Monarchs controlled most the game from here. At 9:46 of the second period, Colton Yellowhorn of the Monarchs got his 5th of the year, after be recalled by the Monarchs from the Ontario Reign. Yellowhorn led the ECHL in who had 36 goals halfway through his season. Colton collected a beautiful pass from Brandon Kozun, which is arguably the goal of the year for the Monarchs. The Monarchs would end up putting another on the board to tie it up at 3-3 when Bears defenseman, Garret Stafford, went to the penalty box for cross-checking giving the Monarchs a power play opportunity with 1:20 remaining in the second. It looked like the second would be over but with 0.01 seconds to go Monarchs center Jordan Weal took a shot from the bottom left point went off Grubauer and in. The Monarchs led the shot in the second 17-8.
The Monarchs opened the scoring at 13:37 mark of the third with another goal from Yellowhorn who tapped it in out of mid-air past Grubauer, who thought that should have been no goal since Kozun was in the crease. In less than two minutes from that goal, Linden Vey scored his first of the night less than 1:11 after Yellowhorn's goal giving the Monarchs a 5-3 lead and 5 unanswer goals. Only 1:55 after Vey scored the Bears finally answered with a goal from Peter Leblanc, cutting the Monarchs lead by one. Bears made a time-out and pulled Grubauer for an empty net to the Monarchs. The bears put shots on Jones with less than a minute to go. The Monarchs finally got the puck out of there zone and Vey stuffed the puck in for the empty-netter sealing the comeback victory 6-4. The three stars all came from the Monarchs, third was Kozun with 2 assists, second was Vey with 2 goals and a much deserving first star, Yellowhorn who had2 goals on the night.
The Bears fell to 30-25-3 and are still 8th in the Eastern Conference and the Monarchs improve to 30-27-2 and are 2 points out of 8th of the Eastern Conference playoff race, they will play Sunday afternoon against the Worcester Sharks. The Manchester Monarchs will play Sunday afternoon at the Verizon Wireless Arena in Manchester, NH against the St. Johns IceCaps (26-33-1) who find themselves 14th in the Eastern Conference. With a Monarchs win and a Bears loss the monarchs can propel themselves into 8th in the Eastern Conference.
Justin Cummings
firstname.lastname@example.com overcome 3-0 deficit to win


text:
- Why fight over free trade confounds partisan divide
- Still no state budget
- Crime control is not the responsibility of landlords
- Fly over to the Poplar Grove Wings and Wheels Museum benefit
- Local leaders warn of budget deadlock's impact
- SHUTDOWN: Illinois preps for the worst
- TRRT Online Edition | July 1-7
- Governor, AG differ on legality of payroll without budget
- Regular RHA meeting a quiet affair
- Funnel clouds possible through evening
Comptroller: 'Obamacare' could cost state as much as $2.4 billion over six years as more enroll in Medicaid
Online Staff Report CHICAGO — Illinois Comptroller Judy Baar Topinka (R) warned lawmakers June 28 that the Supreme Court's ruling to uphold the federal Patient Protection and Affordable Care Act, informally known as "Obamacare," could lead to...
- Posted June 28, 2012
'Obamacare' narrowly upheld by Supreme Court in 5-4 decision
By Shauna Ubersox Staff Writer In a close 5-4 ruling Thursday, June 28, the Supreme Court of the United States voted to uphold the Patient Protection and Affordable Care Act, informally known as "Obamacare." The law states...
- Posted June 28, 2012
Chicago's NATO costs still being tabulated
By Jayette Bolinski and Stephanie Fryer Illinois Statehouse News CHICAGO — It's been more than a month since Chicago hosted the international NATO Summit and its accompanying protesters, but details continue to trickle out about the cost...
- Posted June 28, 2012
Japanese view of gardens topic of June 28 event at Anderson Japanese Gardens
Online Staff Report Westerners often think of home and garden as two separate things, using different words to describe "inside" and "outside" and placing a thick wall between the two. In Japan, however, the home and the...
- Posted June 27, 2012
Regardless of Supreme Court ruling on 'Obamacare,' health care costs going up
By Andrew Thomason Illinois Statehouse News SPRINGFIELD, Ill. — Listening to experts and advocates of all political stripes, it seems health care costs are going to go up, no matter how the U.S. Supreme Court rules on...
- Posted June 27, 2012
Madigan, states announce settlement over deceptive exploitation of veterans' education benefits
Online Staff Report WASHINGTON, D.C. — Illinois Attorney General Lisa Madigan (D) joined several of her counterparts, U.S. senators and federal officials June 27 to announce a settlement with a California-based company over allegations that its website,...
- Posted June 27, 2012
Rock River Valley Blood Center in need of blood donors prior to July 4 holiday
Online Staff Report To ensure an adequate summer blood supply, Rock River Valley Blood Center (RRVBC) is asking healthy individuals to donate blood leading up to the Fourth of July holiday. Whole blood and platelet donors and...
- Posted June 27, 2012
IEPA to release ground scan results around Amerock plant
By Richard S. Gubbe Contributing Writer Results from the ground scan completed by the Illinois Environmental Protection Agency (IEPA) on land owned by the Rockford Park District and Northwest Community Center (NWCC) will be released soon, according...
- Posted June 27, 2012
Midwest Museum of Natural History is Rockin' for the Reptiles
Staff Report SYCAMORE, Ill. — Midwest Museum of Natural History (MMNH) in Sycamore, Ill., is home to scaly critters of all shapes and sizes. From boa constrictors to tortoises, these creepy crawly residents are a favorite of...
- Posted June 27, 2012
Baseball: RiverHawks' road woes continue
By Bill Smith LOVES PARK, Ill. — The Rockford RiverHawks took two of three games from the Gateway Grizzles at home, but lost two of three on the road at Normal and fell in the first two...
- Posted June 27, 2012


text:
Hi!Thanks for processing my order last week! It was very quick and easy. I am
impressed with your fine service and my friends said the lobster was
outstanding! Many thanks!Kathryn Pabich
Creme Fraiche, crafted by Jennifer at the Silvery Moon Creamery, has a rich buttery texture with a delicate tang that is sure to provide a tantalizing bed for our fine Caviar spread on crackers or blini.


text:
Out of Stock
© 2015 Replacements, Ltd. All rights reserved.
With Our "Find This For Me" Service we notify you via email once we have stock!
Piece Code: TRB4
Piece Name: 4" Triangular Bowl
Size: 4 5/8 in
© 2015 Replacements, Ltd. All rights reserved
Piece Code: CRBC5
Piece Name: 5 Inch Round Crimped Bowl
Size: 5 1/2 in
Piece Code: CRBC9
Piece Name: 9" Round Crimped Bowl
Size: 9 in
Special Characteristics:
Piece Code: LFAICB
Piece Name: Fairy Lamp with Ceramic Base
Size: 3 3/4 in
Special Characteristics:
Piece Code: LFAIGL
Piece Name: Fairy Lamp Globe
Size: 2 3/4 in
Piece Code: LFACBA
Piece Name: Fairy Lamp-Ceramic Base
Size: 1 5/8 in
Piece Code: TPH
Piece Name: Toothpick Holder
Piece Code: VJACK
Piece Name: Jack in the Pulpit Vase
Size: 7 3/8 in
Special Characteristics:
Piece Code: VATR10
Piece Name: 10" Trumpet, Vase
Size: 10 3/8 in
Special Characteristics:


text:
Disclosed are compositions and methods for alleviating the problem of reaction of lithium or other alkali or alkaline earth metals with incompatible processing and operating environments by creating a ionically conductive chemical protective layer on the lithium or other reactive metal surface. Such a chemically produced surface layer can protect lithium metal from reacting with oxygen, nitrogen or moisture in ambient atmosphere thereby allowing the lithium material to be handled outside of a controlled atmosphere, such as a dry room. Production processes involving lithium are thereby very considerably simplified. One example of such a process in the processing of lithium to form negative electrodes for lithium metal batteries.
1. A stand alone metallic negative electrode, comprising:
an alkali metal layer having a first surface; and
a chemical protective layer coating the first surface, which protective layer comprises an alkali or alkaline earth metal carbonate.
2. The electrode of
3. The electrode of
4. The electrode of
5. The electrode of
6. The electrode of
7. The electrode of
8. The electrode of
9. The electrode of
10. The electrode of
11. The electrode of
12. The electrode of
13. The electrode of
14. The electrode of
15. The electrode of
16. The electrode of
17. The electrode of
18. The electrode of
19. The electrode of
20. The electrode of
21. The electrode of
22. A method of providing a chemical protective layer on a metal, comprising:
introducing an alkali metal into a reaction chamber;
introducing one or more precursors of the protective layer into the reaction chamber and into contact with a first surface of the metal; and
conducting a reaction involving the one or more precursors to form the chemical protective layer on the metal;
wherein the protective layer comprises an alkali or alkaline earth metal carbonate.
23. The method of
24. The method of
25. The method of
26. The method of
27. The method of
28. The method of
29. The method of
30. The method of
31. The method of
32. The method of
33. The method of
34. The method of
35. The method of
36. The method of
37. The method of
38. The method of
39. The method of
40. The method of
41. The method of
42. The method of
43. A method of providing a chemical protective layer on a negative metal electrode, comprising:
forming and placing in a battery cell package an electrochemical structure comprising,
a negative electrode comprising an alkali metal,
a positive electrode,
a separator disposed between the negative and positive electrodes, and
current collectors on the negative and positive electrodes;
introducing a liquid electrolyte or catholyte comprising one or more precursors of a protective layer into the battery cell package and into contact with an exposed surface of the negative metal electrode; and
conducting a reaction involving the one or more precursors to form the chemical protective layer on the exposed surface of the negative metal electrode;
wherein the protective layer comprises an alkali or alkaline earth carbonate.
44. The method of
45. The method of
46. The method of
47. The method of
48. The method of
49. A battery cell, comprising:
an negative metal electrode a negative electrode comprising an alkali metal and having a protective layer on an electrolyte exposed surface;
a positive electrode chosen from a sulfur-based positive electrode, a metal oxide based positive electrode, and a metal sulfide based positive electrode;
an electrolyte disposed between the negative and positive electrodes; and
current collectors on the negative and positive electrodes;
wherein the protective layer comprises an alkali or alkaline earth metal carbonate.
50. The battery cell of
51. The battery cell of
52. The battery cell of
53. The battery cell of
54. The battery cell of
55. The electrode of
56. The electrode of
57. The electrode of
58. The method of
59. The method of
60. The method of
This application claims priority to U.S. Provisional Patent Application No. 60/342,326 filed Dec. 21, 2001, titled CHEMICAL PROTECTION OF A LITHIUM SURFACE. This provisional patent application is incorporated herein by reference for all purposes.
1. Field of the Invention
The present invention relates generally to surface treatments to facilitate the processing of lithium (or other alkali) metal or alloys, such as for incorporation in electrochemical devices.
2. Description of Related Art
Lithium is an attractive material for use as an electrode component in electrochemical devices, such as batteries and capacitors, due to its very high energy density and low equivalent weight. However, lithium is highly reactive in ambient conditions and thus requires special handling during processing. Typically, lithium battery manufacture is conducted in inert environments in order to guard against degradation of lithium until it is hermetically sealed within a battery cell container.
Even with these precautions, lithium may detrimentally react with incompatible materials in the processing environment. For example, rechargeable lithium metal batteries have been prone to cell cycling problems. On repeated charge and discharge cycles, lithium "dendrites" have been found to gradually grow out from the lithium metal electrode, through the electrolyte, and ultimately contact the positive electrode. This causes an internal short circuit in the battery, rendering the battery unusable after a relatively few cycles. While cycling, lithium electrodes may also grow "mossy" deposits which can dislodge from the negative electrode and thereby reduce the battery's capacity. To address these problems, some researchers have proposed that the electrolyte facing side of the lithium negative electrode be coated with a "protective layer." Several methods may be envisioned for producing such a protective layer, but the processing methods by which such layers are produced may not be compatible with the lithium metal.
Some research has focused on "nitridation" of the lithium metal surface as a means for protecting lithium electrodes. In such process, a bare lithium metal electrode surface is reacted with a nitrogen plasma to form a surface layer of polycrystalline lithium nitride (Li3N). This nitride layer conducts lithium ions and at least partially protects the bulk lithium of the negative electrode from a liquid electrolyte. A process for nitriding lithium battery electrodes it is described in R&D Magazine, September 1997, p. 65 (describing the work of S. A. Anders, M. Dickinson, and M. Rubin at Lawrence Berkeley National Laboratory). Unfortunately, in addition to structural and electrical problems with this approach, lithium nitride decomposes when exposed to moisture. While lithium metal batteries employ nonaqueous electrolytes, it is very difficult to remove all traces of moisture from the electrolyte. Thus, trace moisture will ultimately compromise the protective properties of the lithium nitride.
Other pre-formed lithium protective layers have been contemplated. Most notably, U.S. Pat. No. 5,314,765 (issued to Bates on May 24, 1994) describes a lithium electrode containing a thin layer of sputtered lithium phosphorus oxynitride ("LiPON") or related material. LiPON is a single ion (lithium ion) conducting glass. It is typically deposited by reactive sputtering of a lithium phosphate in the presence of nitrogen. The nitrogen, however, attacks the lithium surface, thereby making the process of direct deposition of the glass film impossible.
Other examples of potential protective layers may include the deposition of polymer layers that involve solvents or monomers that are incompatible with lithium.
Accordingly, it would facilitate handling of metallic lithium, lithium alloy or other alkali metal or metal alloys to provide an adequate surface protective layer. In particular fabrication processing and successful operation of alkali metals as battery electrodes would be enhanced by the provision of such a protective layer.
The present invention alleviates the problem of reaction of lithium or other alkali or alkaline earth metals with incompatible processing and operating environments by creating a ionically conductive chemical protective layer on the lithium or other reactive metal surface. Such a chemically produced surface layer can protect lithium metal from reacting with oxygen, nitrogen or moisture in ambient atmosphere thereby allowing the lithium material to be handled outside of a controlled atmosphere, such as a dry room. Production processes involving lithium are thereby very considerably simplified. One example of such a process is the processing of lithium to form negative electrodes for lithium metal batteries.
In one aspect, the invention relates to a composition comprising a lithium or other alkali or alkaline earth metal layer having a surface coated with a chemical protective layer, which protective layer is, at least transiently, physically and chemically stable in an ambient air environment and protects the lithium metal from further chemical reaction, which protective layer is covalently bonded to the metal surface, and which protective layer conducts ions of the metal. In a preferred embodiment, the metal layer is lithium or a lithium alloy and forms part of a negative battery electrode.
In another aspect, the invention relates to a method of providing a chemical protective layer on a surface of a lithium or other alkali or alkaline earth metal. The method includes introducing the lithium or other reactive metal into a reaction chamber, introducing one or more precursors of the protective layer into the reaction chamber and into contact with the metal, and conducting a reaction involving the one or more precursors to form the chemical protective layer on the metal surface, wherein the protective layer is, at least transiently, physically and chemically stable in an ambient air environment and protects the metal surface from further chemical reaction, the protective layer is covalently bonded to the surface, and the protective layer conducts ions of the metal.
In preferred embodiments, the chemical protective layer may be a phosphate or a carbonate. It may be formed by a liquid, vapor or gas phase surface treatment with a chemical precursor. It may be formed ex situ or in situ (for example, by incorporation of a protective layer-forming chemical precursor in an electrolyte) in a battery cell. Application of the chemical protective layer may be followed by application of a glassy protective layer, such as LiPON, and facilitates this process.
These and other features of the invention will further described below.
Reference will now be made in detail to specific embodiments of the invention. Examples of the specific embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order not to unnecessarily obscure the present invention.
The present invention alleviates the problem of reaction of lithium or other alkali or alkaline earth metals with incompatible processing and operating environments by creating a ionically conductive chemical protective layer on the lithium or other reactive metal surface. Such a chemically produced surface layer can protect lithium metal from reacting with oxygen, nitrogen or moisture in ambient atmosphere thereby allowing the lithium material to be handled outside of a controlled atmosphere, such as a dry room. Production processes involving lithium are thereby very considerably simplified. One example of such a process is the processing of lithium to form negative electrodes for lithium metal batteries.
The present invention will be described herein primarily with reference to a lithium metal battery electrode, a preferred embodiment. However, it should be understood that methods and compositions described may be equally applicable to other alkali metals (e.g., sodium and potassium) or alloys, or alkaline earth metals (e.g., calcium or magnesium) or alloys, as would be apparent to one of skill in the art. Also, the invention may be applicable more generally to lithium metal substrates used in other electrochemical or non-electrochemical devices or compositions.
Techniques and equipment for forming and coating lithium metal substrates, for example for use as negative battery electrodes, are known in the art and will not be further described here in order not to unnecessarily obscure the present invention. For example, U.S. Pat. No. 6,025,094, entitled PROTECTIVE COATINGS FOR NEGATIVE ELECTRODES, to Visco et al., incorporated by reference herein in its entirety and for all purposes, describes lithium metal battery electrode and cell fabrication techniques application to implement the present invention.
In accordance with the present invention, the surface of a metallic negative electrode is modified to include a chemical protective layer on the electrolyte side. This protective layer should be at least transiently physically and chemically stable in an ambient air environment and protect the lithium metal from further chemical reaction, be covalently bonded to the first surface, and conduct lithium ions. The protective layer may be pre-formed (prior to battery fabrication) or formed in situ (e.g., incorporated in electrolyte). In the description that follows, the invention is described in terms of certain specific compositions, configurations, and processes to help explain how it may be practiced. The invention is not limited to these specific embodiments.
Backing layer 14 is provided on the side of negative electrode 10 which faces away from the electrolyte. It should be electronically conductive and unreactive to moisture, gases in the atmosphere (e.g., oxygen and carbon dioxide), electrolytes and other agents it is likely to encounter prior to, during, and after fabrication of a battery. In addition, backing material 14 should be compatible with the metal in layer 16 at potentials encountered in the battery. In this regard, the material in backing layer 18 should not easily migrate into or otherwise detrimentally effect the electrochemical properties of metal layer 16. Examples of suitable materials for backing layer 14 include foils or other thin metal layers of copper, stainless steel, nickel, zinc, chromium, and compatible alloys thereof. In addition, such metals may be provided as metallization layers on plastics such as polyethylene terephthalate (PET), polypropylene, polyethylene, polyvinylchloride (PVC), polyolefins, polyimides, etc.
In an alternative embodiment, conductive backing layer 14 is replaced with a non-electronically conductive outer layer such as a second protective layer. In this embodiment, a current collector or terminal must still be affixed to the alkali metal electrode. This may take the form of a metal tab or other electronically conductive member that extends beyond the protective layers.
Most generally, metal layer 16 can comprise any metal, any mixture of metal capable of functioning as a negative electrode. However, the protective layers of this invention will find most use in protecting highly reactive metals such as alkali metals and alkaline earth metals.
In one preferred embodiment, the materials for the negative electrodes include a metal such lithium or sodium or an alloy of one of these with one or more additional alkali metals (e.g., potassium) and/or alkaline earth metals (e.g., calcium and magnesium). Preferred alloys include lithium aluminum alloys, lithium silicon alloys, lithium tin alloys, and sodium lead alloys (e.g., Na4Pb).
As indicated above, protective layer 18 should form a continuous and intimate interface with metal layer 16 to protect it from various agents in the environment. Unfortunately, most alkali metals are so reactive that very soon after they are produced in pure form, their surfaces react with any moisture, oxygen, and carbon dioxide in the environment. Even when handled in a dry box, lithium typically develops a thin layer of oxide, hydroxide, carbonate, etc. Unfortunately, such materials may hamper formation of a highly protective glass surface layer. As will be explained in more detail below, preferred processes of this invention form chemical protective layers.
Thereafter, other protective layers (e.g., inorganic ionically conductive glass, such as LiPON) may be formed directly on the chemically protected alkali metal surfaces immediately after the chemical protective layer is itself formed—possibly in a single vacuum chamber—or in a separate chamber—with the chemical protective layer providing protection to the metal surface during the intervening period.
Creation of a thin preferably between about 1 nm and 10 microns, more preferably between 10 nm and 1 micron, even more preferably between 50 nm and 0.1 micron, chemically protective layer on the lithium or other reactive metal surface helps to solve the problem of reaction of the metal surface with incompatible processing environment, in particular, in ambient conditions containing oxygen, nitrogen or moisture, or with gaseous nitrogen during direct deposition of a LiPON glass layer onto lithium by reactive sputtering of lithium phosphate.
The chemical protective layer 18 may be composed of any suitable material that reacts with lithium without degrading its surface (i.e., the reaction product does not block lithium ion transport) to form a coating that prevents further reaction. Particularly preferred examples include ionically conductive metal salts such as carbonates, phosphates, metaphosphates, phosphites, dithionates, fluorides, metasilicates and orthosilicates. In specified embodiments, lithium phosphate or lithium carbonate on lithium or lithium alloy surfaces are used.
Such coatings may be permanent or transient, depending on the quality of the lithium surface being coated. For example, a very high quality surface, that is, one that is flat and smooth, will support a longer lasting or permanent coating. A lower quality, rougher surface may only support a coating having a briefer lifetime. However, even a coating providing transient protection (e.g., a few hours or even minutes) may provide a significant advantage in handling and processing highly reactive materials such as lithium. For example, a coating that is effective long enough to move the substrate from one reaction chamber to another or through one or more process steps that would otherwise result in deleterious reaction of the lithium with components of the ambient or process environment is very advantageous.
Chemical protective coatings in accordance with the present invention should be applied in a controlled environment, free of materials that would react deleteriously with lithium, such as a processing chamber or glove box, as are well known to those of skill in the art. The coatings may be applied by reaction of the lithium with liquid, vapor or gas phase precursors. The use of vapor or gas phase precursors may be particularly advantageous to facilitate single chamber processing of lithium.
Referring to the flow chart of
Protective layer precursors may be contacted with reactive metal surfaces in liquid, vapor or gas phase according to various techniques such as are well known in the art.
In one specific embodiment, a layer of lithium phosphate may be formed chemically by bringing the lithium surface into contact with anhydrous phosphoric acid in a suitable organic solvent. Examples of organic solvents suitable for incorporation of phosphate forming additives such as anhydrous phosphoric acid, are DME, various glymes (e.g., mono-, di- and tri-glymes), ether, and other compatible aprotic solvents, such as THF, commonly know in the field. Concentrations of anhydrous phosphate forming additives may range from 5 ppm to 30 vol % of the solvent.
Alternatively, a layer of phosphate may be formed by vapor-based processes such as sputtering or electron beam deposition, organometallic methods, sol-gel methods, or any other methods such as commonly known for forming thin layers on surfaces, such as described further below. In other embodiments, a layer of lithium carbonate may be formed by bringing the lithium metal surface into contact with gaseous CO2, CO2 and O2 mixtures, or liquid organic carbonates, in particular, alkyl carbonates (propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and others).
Other possible protective layers include lithium metaphosphate (LiPO3), lithium dithionate (Li2S2O4), lithium fluoride (LiF), lithium metasilicate (Li2SiO3), and Lithium orthosilicate (Li2SiO4), which could be reacted with the lithium (or other) metal surface in the acid form, (e.g., HF+lithium metal=lithium metal-LiF+H2 evolution).
A variety of processes may be used to form a chemical protective layer on an active metal (e.g., lithium) surface in accordance with the present invention. These include:
Vapor phase processes, in which a gas (e.g., CO2 or SO2 (plus small amount of O2)) is introduced into a chamber containing a lithium metal foil. The lithium surface reacts with the CO2 to form Li2CO3, or with SO2 to form Li2SO4 or Li2S2O4. For a phosphorus-based film, red phosphorus may be sublimed in the presence of oxygen to form lithium phosphate on the surface of the lithium;
Organometallic processes in which an organic molecule containing phosphorus, sulfur, fluorine, etc. are dissolved in an organic solvent. The solution is contacted with lithium in a suitable processing environment and allowed to react with the lithium to form LiF, Li3PO4, Li2SO4, etc. (e.g., MeO3P+Li→Li3PO4+MeOH);
Sol-gel processes in which a glass and/or ceramic precursor dissolved in an organic solvent, such as tetraethylorthosilicate (TEOS) in DME, is aerosol-sprayed, dip-coated, or spun onto a lithium surface, allowing reaction with the lithium surface to form an ionically conductive lithium silicate glass (e.g., Li4SiO4);
Sputtering processes in which a protective layer precursor is sputtered onto to a lithium surface in an inert sputtering environment, such as provided by pure argon, to form the protective layer (e.g., Li3PO4 or LF); and
Electron beam processes in which an e-beam is used to evaporate a protective layer precursor to form the protective layer (e.g., Li3PO4 or LF).
Further, as noted above, protection of the lithium (or other metal) surface may also be improved by incorporation of a chemical protective layer precursor (e.g., phosphoric acid) directly into the electrolyte or catholyte of a lithium anode battery, for example in an amount of about 5 ppm-30 vol. %, preferably from 5 ppm to 5000 ppm, more preferably form 100 to 3000 ppm, even more preferably from 500 to 2000 ppm. Referring to
In situ protection in batteries and related electrochemical devices of the preformed protective surface layer may be further enhanced by incorporating such precursors in the electrolyte of such battery or device.
Where the invention is implemented as a negative electrode for a lithium (or other alkali) metal battery it may be desirable to provide a further physical protective coating on the electrode. As noted above, the chemical protective layer of the present invention advantageously provides protection for the lithium from deleterious reactions with incompatible processing environments (for example, ambient air atmospheres containing oxygen, nitrogen (particularly in the case of LiPON deposition) or moisture) by creating a chemical protective layer on the lithium metal surface. This allows the lithium material to be handled outside of a controlled atmosphere, such as a dry room, facilitating application of a physical protective layer, such as a glass or amorphous material that is conductive to alkali metal ions of the alkali metal comprising layer 16. Examples of such glassy protective layer materials are provided in U.S. Pat. No. 6,025,094, previously incorporated by reference. Preferred types of inorganic ionically conductive glass include phosphorus-based glass, oxide-based glass, sulphur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium based glass, and glass-ceramic active metal ion conductors, sodium beta-alumina or lithium beta-alumina. Examples of suitable ionically conductive protective glasses include lithium phosphorus oxynitride (LiPON), Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3 and Li1-x-yAlxTi2-xSiyP3-yO12, LISICON, NASICON, sodium and lithium beta-alumina. These protective glasses may also act as a solid electrolyte where the metal is used as a negative electrode in a battery cell. Such an electrode may also alternatively be combined with a solid polymer electrolyte.
As noted above, it is further contemplated that chemical protective layer precursors may be incorporated in the electrolytes of battery cells having negative alkali metal electrodes with glassy protective layers, such as LiPON. The presence of such precursors allows for the formation of a "healing" chemical protective layer in the event of a crack or other defect or damage to the glassy protective layer.
Referring now to
An optional separator in region 416 prevents electronic contact between the positive and negative electrodes. A positive electrode 418 abuts the side of separator layer 416 opposite negative electrode 414. As electrolyte region 416 is an electronic insulator and an ionic conductor, positive electrode 418 is ionically coupled to but electronically insulated from negative electrode 414. Finally, the side of positive electrode 418 opposite electrolyte region 416 is affixed to a positive current collector 420. Current collector 420 provides an electronic connection between a positive cell terminal (not shown) and positive electrode 418.
Current collector 420, which provides the current connection to the positive electrode, should resist degradation in the electrochemical environment of the cell and should remain substantially unchanged during discharge and charge. In one embodiment, the current collectors are sheets of conductive material such as aluminum or stainless steel. The positive electrode may be attached to the current collector by directly forming it on the current collector or by pressing a pre-formed electrode onto the current collector. Positive electrode mixtures formed directly onto current collectors preferably have good adhesion. Positive electrode films can also be cast or pressed onto expanded metal sheets. Alternately, metal leads can be attached to the positive electrode by crimp-sealing, metal spraying, sputtering or other techniques known to those skilled in the art. Some positive electrode can be pressed together with the electrolyte separator sandwiched between the electrodes. In order to provide good electrical conductivity between the positive electrode and a metal container, an electronically conductive matrix of, for example, carbon or aluminum powders or fibers or metal mesh may be used.
A separator may occupy all or some part of electrolyte compartment 416. Preferably, it will be a highly porous/permeable material such as a felt, paper, or microporous plastic film. It should also resist attack by the electrolyte and other cell components under the potentials experienced within the cell. Examples of suitable separators include glass, plastic, ceramic, and porous membranes thereof among other separators known to those in the art. In one specific embodiment, the separator is Celgard 2300 or Celgard 2400 available from Hoechst Celanese of Dallas, Tex.
In an alternative embodiment, no separator is employed and a solid electrolyte or glassy protective layer, such as LiPON, on the negative electrode prevents the positive and negative electrodes from contacting one another and serves the function of a separator. In such cases, the protective layer should be tough. It may be relatively thick and made from a material that resists cracking and abrasion.
In some embodiments of the invention, the cell may be characterized as a "thin film" or "thin layer" cell. Such cells possess relatively thin electrodes and electrolyte separators. Preferably, the positive electrode is no thicker than about 300 μm, more preferably no thicker than about 150 μm, and most preferably no thicker than about 100 μm. The negative electrode preferably is no thicker than about 100 μm and more preferably no thicker than about 100 μm. Finally, the electrolyte separator (when in a fully assembled cell) is no thicker than about 100 μm and more preferably no thicker than about 40 μm.
Sulfur positive electrodes and metal-sulfur batteries are described in U.S. Pat. No. 5,686,201 issued to Chu on Nov. 11, 1997 and U.S. patent application Ser. No. 08/948,969 naming Chu et al. as inventors, filed on Oct. 10, 1997. Both of these documents are incorporated by reference for all purposes. The sulfur positive electrodes preferably include in their theoretically fully charged state sulfur and an electronically conductive material. At some state of discharge, the positive electrode will include one or more polysulfides and possibly sulfides, which are polysulfides and sulfides of the metal or metals found in the negative electrode. In some embodiments, the fully charged electrode may also include some amount of such sulfides and/or polysulfides.
The positive electrode is fabricated such that it permits electrons to easily move between the sulfur and the electronically conductive material, and permits ions to move between the electrolyte and the sulfur. Thus, high sulfur utilization is realized, even after many cycles. If the lithium-sulfur battery employs a solid or gel state electrolyte, the positive electrode should include an electronic conductor (e.g., carbon) and an ionic conductor (e.g., polyethylene oxide) in addition to the sulfur electroactive material. If the battery employs a liquid electrolyte, the positive electrode may require only an electronic conductor in addition to the sulfur electroactive material. The electrolyte itself permeates the electrode and acts as the ionic conductor. In the case of a liquid electrolyte cell, the battery design may assume two formats: (1) all active sulfur (elemental sulfur, polysulfides and sulfides of the positive electrode) is dissolved in electrolyte solution (one phase positive electrode) and (2) the active sulfur is distributed between a solid phase (sometimes precipitated) and a liquid phase.
When the lithium-sulfur battery cells in accordance with this invention include a liquid electrolyte, that electrolyte should keep many or all of sulfur discharge products in solution and therefore available for electrochemical reaction. Thus, they preferably solubilize lithium sulfide and relatively low molecular weight polysulfides. In a particularly preferred embodiment, the electrolyte solvent has repeating ethoxy units (CH2CH2O). This may be a glyme or related compound. Such solvents are believed to strongly coordinate lithium and thereby increase the solubility of discharge products of lithium-sulfur batteries. Suitable liquid electrolyte solvents are described in more detail in U.S. patent application Ser. No. 08/948,969, previously incorporated by reference.
It should be understood that the electrolyte solvents of this invention may also include cosolvents. Examples of such additional cosolvents include sulfolane, dimethyl sulfone, dialkyl carbonates, tetrahydrofuran (THF), dioxolane, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), butyrolactone, N-methylpyrrolidinone, dimethoxyethane (DME or glyme), hexamethylphosphoramide, pyridine, N,N-diethylacetamide, N,N-diethylformamide, dimethylsulfoxide, tetramethylurea, N,N-dimethylacetamide, N,N-dimethylformamide, tributylphosphate, trimethylphosphate, N,N,N′,N′-tetraethylsulfamide, tetraethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine, methanol, ethylene glycol, polyethylene glycol, nitromethane, trifluoroacetic acid, trifluoromethanesulfonic acid, sulfur, dioxide, boron trifluoride, and combinations of such liquids.
The protective layers employed in this invention may allow the use of electrolyte solvents that work well with sulfides and polysulfides but may attack lithium. Examples of solvents in this category include amine solvents such as diethyl amine, ethylene diamine, tributyl amine, amides such as dimethyl acetamide and hexamethyl phosphoramide (HMPA), etc.
Exemplary but optional electrolyte salts for the battery cells incorporating the electrolyte solvents of this invention include, for example, lithium trifluoromethanesulfonimide (LiN(CF3SO2)2), lithium triflate (LiCF3SO3), lithium perchlorate (LiClO4), LiPF6, LiBF4, and LiAsF6, as well as corresponding salts depending on the choice of metal for the negative electrode, for example, the corresponding sodium salts. As indicated above, the electrolyte salt is optional for the battery cells of this invention, in that upon discharge of the battery, the metal sulfides or polysulfides formed can act as electrolyte salts, for example, Mx/zS wherein x=0 to 2 and z is the valence of the metal.
As mentioned, the battery cells of this invention may include a solid-state electrolyte. An exemplary solid-state electrolyte separator is a ceramic or glass electrolyte separator which contains essentially no liquid. Specific examples of solid-state ceramic electrolyte separators include beta alumina-type materials such as sodium beta alumina, Nasicon™ or Lisicon™ glass or ceramic. Polymeric electrolytes, porous membranes, or combinations thereof are exemplary of a type of electrolyte separator to which an aprotic organic plasticizer liquid can be added according to this invention for the formation of a solid-state electrolyte separator generally containing less than 20% liquid. Suitable polymeric electrolytes include polyethers, polyimines, polythioethers, polyphosphazenes, polymer blends, and the like and mixtures and copolymers thereof in which an appropriate electrolyte salt has optionally been added. Preferred polyethers are polyalkylene oxides, more preferably, polyethylene oxide.
In the gel-state, the electrolyte separator generally contains at least 20% (weight percentage) of an organic liquid (see the above listed liquid electrolytes for examples), with the liquid being immobilized by the inclusion of a gelling agent. Many gelling agents such as polyacrylonitrile, polyvinylidene difluoride (PVDF), or polyethylene oxide (PEO), can be used.
It should be understood that some systems employing liquid electrolytes are commonly referred to as having "polymer" separator membranes. Such systems are considered liquid electrolyte systems within the context of this invention. The membrane separators employed in these systems actually serve to hold liquid electrolyte in small pores by capillary action. Essentially, a porous or microporous network provides a region for entraining liquid electrolyte. Such separators are described in U.S. Pat. No. 3,351,495 assigned to W.R. Grace & Co. and U.S. Pat. Nos. 5,460,904, 5,540,741, and 5,607,485 all assigned to Bellcore, for example. Each of these patents is incorporated herein by reference for all purposes.
The fully charged state of some cells of this invention need not require that the positive electrode be entirely converted to elemental sulfur. It may be possible in some cases to have the positive electrode be a highly oxidized form of lithium polysulfide, for example, as in Li2Sx where x is five or greater. The fully charged positive electrode may also include a mixture of such polysulfides together with elemental sulfur and possibly even some sulfide. It should be understood that during charge, the positive electrode would generally not be of uniform composition. That is, there will be some amount of sulfide, sulfur, and an assortment of polysulfides with various values of x. Also, while the electrochemically active material includes some substantial fraction of "sulfur," this does not mean that the positive electrode must rely exclusively upon sulfur for its electrochemical energy.
The electronic conductor in the positive electrode preferably forms an interconnected matrix so that there is always a clear current path from the positive current collector to any position in the electronic conductor. This provides high availability of electroactive sites and maintained accessibility to charge carriers over repeated cycling. Often such electronic conductors will be fibrous materials such as a felt or paper. Examples of suitable materials include a carbon paper from Lydall Technical Papers Corporation of Rochester, N.H. and a graphite felt available from Electrosynthesis Company of Lancaster, N.Y.
The sulfur is preferably uniformly dispersed in a composite matrix containing an electronically conductive material. Preferred weight ratios of sulfur to electronic conductor in the sulfur-based positive electrodes of this invention in a fully charged state are at most about 50:1, more preferably at most about 10:1, and most preferably at most about 5:1. The sulfur considered in these ratios includes both precipitated or solid phase sulfur as well as sulfur dissolved in the electrolyte. Preferably, the per weight ratio of electronic conductor to binder is at least about 1:1 and more preferably at least about 2:1.
The composite sulfur-based positive electrode may further optionally include performance enhancing additives such as binders, electrocatalysts (e.g., phthalocyanines, metallocenes, brilliant yellow (Reg. No. 3051-11-4 from Aldrich Catalog Handbook of Fine Chemicals; Aldrich Chemical Company, Inc., 1001 West Saint Paul Avenue, Milwaukee, Wis.) among other electrocatalysts), surfactants, dispersants (for example, to improve the homogeneity of the electrode's ingredients), and protective layer forming additives to protect a lithium negative electrode (e.g., organosulfur compounds, phosphates, iodides, iodine, metal sulfides, nitrides, and fluorides). Preferred binders (1) do not swell in the liquid electrolyte and (2) allow partial but not complete wetting of the sulfur by the liquid electrolyte. Examples of suitable binders include Kynar available from Elf Atochem of Philadelphia, Pa., polytetrafluoroethylene dispersions, and polyethylene oxide (of about 900 k molecular weight for example). Other additives include electroactive organodisulfide compounds employing a disulfide bond in the compound's backbone. Electrochemical energy is generated by reversibly breaking the disulfide bonds in the compound's backbone. During charge, the disulfide bonds are reformed. Examples of organodisulfide compounds suitable for use with this invention are presented in U.S. Pat. Nos. 4,833,048 and 4,917,974 issued to De Jonghe et al. and U.S. Pat. No. 5,162,175 issued to Visco et al.
Various experiments were conducted to demonstrate the advantages provided by the various aspects of this invention. The examples presented here are intended to better illustrate the invention as described herein and are non-limiting.
Production of Protective Lithium Phosphate Film by Li Surface Treatment with Phosphoric Acid
The Li electrode surface (125 micron foil from Cyprus Foote) was treated with dry DME containing anhydrous phosphoric acid (1500 ppm) for a treatment time of 45 seconds. Surface treatment was conducted by coating of the Li foil pressed onto SS current collector with this solution followed by DME evaporation. About 1.0 ml of the solution was put on Li surface. After Li reaction with phosphoric acid and formation of lithium phosphate layer on the Li surface, DME was allowed to evaporate at room temperature. Residual unreacted phosphoric acid on the surface was rinsed out by a large volume of DME. In some experiments before treatment with phosphoric acid Li surface was polished with Tyvek fabric (1509 B). All described operations were conducted in an argon-filled glove box.
Electrochemical cells containing a Li electrode coated with a lithium phosphate chemical protective underlayer were assembled and tested. The impedance of the interface between the Li electrode and a solution of 0.5 M LiTFSI in the mixture of DME and 1,3-Dioxolane (9:1) was measured after different storage periods. As can be seen from
Production of Protective Lithium Phosphate Underlayer by Li Surface Treatment with Phosphoric Acid
The Li electrode surface (125 μm foil from Cyprus Foote) was treated with dry DME containing anhydrous phosphoric acid as described in Example 1. After the pre-treatment Li foil was transferred to the sputtering chamber for reactive RF sputtering of LiPON glass layer using lithium phosphate target of 8 inch diameter in the presence of nitrogen. RF power was 100 W, and duration of sputtering was about 1.5 hrs. No evidence of reaction between nitrogen and Li and formation of black lithium nitride reaction product was observed and the LiPON layer was successfully deposited onto Li surface. In experiments where described Li pre-treatment with acid was not used, the Li surface was attacked with nitrogen and almost immediately covered with black lithium nitride film. Therefore, Li chemical treatment with phosphoric acid creates a protective underlayer that allows for direct reactive sputtering of LiPON onto Li.
Li/C electrochemical cells containing a Li electrode coated with a lithium phosphate underlayer and the LiPON film produced as described above were assembled and tested. The impedance of the interface between the Li electrode and 10 M sulfur as Li2S8 dissolved in a mixture of DME and 1,3-Dioxolane (9:1) was measured after different periods of storage. As can be seen from
Production of Protective Lithium Phosphate Underlayer by Sputtering of Lithium Phosphate onto Li Surface
The Li electrode (125 micron foil from Cyprus Foote) was transferred to the sputtering chamber and lithium phosphate was sputtered onto the Li surface. Sputtering was conducted in an atmosphere of pure Ar at RF power 100 W. After about 1 hr of sputtering, nitrogen was introduced into the chamber and the LiPON layer about 0.1 micron thick was sputtered onto the Li surface. No evidence of reaction between nitrogen and Li and formation of black lithium nitride reaction product was observed. This demonstrates that Li surface coating with dense lithium phosphate underlayer protects Li surface from nitrogen attack and allows for direct LiPON sputtering onto Li.
Production of Protective Lithium Phosphate Underlayer by Combination of Li Surface Treatment with Phosphoric Acid and Sputtering of Lithium Phosphate onto Li Surface
The Li electrode surface (125 μm foil from Cyprus Foote) was treated with dry DME containing anhydrous phosphoric acid as described in Example 1, then the Li electrode was transferred to the sputtering chamber and lithium phosphate was sputtered onto the Li surface in an atmosphere of pure Ar exactly as described in Example 3. After that Ar was replaced with nitrogen in the sputtering chamber and the LiPON layer about 0.1 micron thick was sputtered onto the Li surface at 100 W. No evidence of reaction between nitrogen and Li and formation of lithium nitride was observed, except for the edges of the Li foil that became black. These edges were coated with the tape and were not exposed during Li treatment with DME containing anhydrous phosphoric acid. As a result, nitrogen reacted with Li along the edges during lithium phosphate sputtering in nitrogen atmosphere.
Incorporation of Phosphoric Acid into the Battery's Catholyte
The desired catholytes were prepared by addition of appropriate amounts (500 and 1500 ppm) of anhydrous phosphoric acid to the solution of 10 M sulfur as Li2S8 in the mixture of DME and 1,3-Dioxolane (9:1). It was shown that the presence of phosphoric acid did not affect the intrinsic stability of the electrolyte system. In particular it did not initiate polymerization of Dioxolane.
Li/C electrochemical cells containing plain Li electrode and the catholytes with and without phosphoric acid were assembled and tested. It was found that the interface impedance for the cells with phosphoric acid additives was small and stable. At the same time the interface impedance for the cells without these additives grew rapidly during storage. This shows that protection of Li surface can be improved by incorporation of phosphoric acid that can react with Li surface forming a protective layer based on lithium phosphate. In the case of Li electrodes coated with the LiPON layer, phosphoric acid may effectively heal cracks which form in the glassy layer during cycling.
Producing Protective Lithium Carbonate Underlayer by Li Surface Treatment with CO2
The Li electrode surface (125 μm foil from Cyprus Foote pressed onto SS current collector) was treated with dry gaseous CO2 (99.99% purity from Matheson Tri-Gas Inc.). Surface treatment was conducted in the specially designed SS reactor. This reactor was loaded with the Li electrodes in the Ar-filled dry box, hermetically sealed, and taken out of the box. The Li electrode surface was treated with CO2 by passing the gas through the reactor for about 30 minutes. During this treatment positive pressure of about 15 psi was maintained inside the reactor. After Li reaction with CO2 and formation of lithium carbonate layer on the Li surface, the Li electrodes were transferred to the sputtering chamber. Reactive RF sputtering of LiPON glass layer was performed in the presence of nitrogen by use lithium phosphate target of 8 inch diameter. RF power was 200 W, and duration of sputtering was about 13 hrs. The Li substrates were rotated during sputtering in order to improve uniformity of the LiPON coating. No evidence of reaction between nitrogen and Li and formation of black lithium nitride reaction product was observed and the LiPON layer was successfully deposited onto Li surface. In experiments where described Li pre-treatment with CO2 was not used, the Li surface was attacked with nitrogen and almost immediately covered with black lithium nitride film. Therefore, Li chemical treatment with gaseous CO2 creates a protective underlayer that allows for direct reactive sputtering of LiPON onto Li.
The chemically protected metal electrodes of the present invention have the advantage that they can be handled in ambient atmosphere without deterioration of the metal electrode surface, and can have additional films deposited onto them in atmospheres that would typically attack the metal surface if it were not for the protective film described herein.
Although the foregoing invention has been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing both the process and compositions of the present invention. For example, while the invention is primarily described with reference to lithium, the chemical protective coatings of the present invention may also advantageously be applied to other alkali metals (e.g., sodium and potassium) and alloys or to alkaline earth metals (e.g., calcium and magnesium) or alloys. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein, but may be modified within the scope and equivalents of the appended claims.
All references cited herein are incorporated by reference for all purposes.
Patent Citations
Referenced by
Legal Events
Original Image


text:
Miguel Galuccio sat quietly with a nervous smile as Argentina's president suddenly thrust the youthful oil executive from obscurity into one of the nation's most high-pressure jobs: leading the newly state-controlled energy company.
BUENOS AIRES, Argentina (AP) -- Miguel Galuccio sat quietly with a nervous smile as Argentina's president suddenly thrust the youthful oil executive from obscurity into one of the nation's most high-pressure jobs: leading the newly state-controlled energy company....
BUENOS AIRES (Reuters) - Argenti
BUENOS AIRES (Reuters) - Argentine President Cristina Fernandez unveiled plans on Monday to seize control of leading energy company YPF, drawing swift warnings from key trade partners and risking the country's further economic isolation. YPF , controlled by Spain's Repsol , has been under intense pressure from Fernandez's center-left government to boost production, and its share price has plunged due to months of speculation about a state takeover. Until recently, YPF had a harmonious relationship with Fernandez, whose increasingly interventionist and off-beat policies infuriate critics. ...
By Jennifer Warren:For all of the shale oil and gas reserves in Argentina, obstacles by way of politics could be trumping progress once again, and giving mixed signals. A recent statement by a Shell (NYSE:RDS.A) (NYSE:RDS.B) executive sums it up:
Husky Energy Inc, Canada's No.3 integrated oil company, swung to a quarterly loss and cut its capital budget for the second time in three months as oil trades at five-year lows.
The company, controlled by Hong Kong billionaire Li Ka-shing, said it expects to spend $3-billion to $3.1-billion in 2015. The company cut its budget by a third to $3.4 billion in December.
Husky joins Cenovus Energy Inc, MEG Energy Corp and other Canadian oil producers, who have lowered capital investments due to a 50% drop in global prices since June.
The discovery of North Sea riches in the 1970s planted the seed of modern-day Scottish nationalism as supporters of independence cried "It's our oil!"
Four decades later, nothing will be more important to the economic future of Scotland than the oil industry should the country vote to end the 307-year union with the rest of the U.K.
For the second time in less than a year, Coastal Energy Corp., a Houston-based, TSX-listed company with assets in Thailand and Malaysia has become the subject of a takeover from a foreign controlled company with links to a foreign government.
This time round, the would-be acquirer — according to documents seen by Financial Post — is Jynwel Capital Limited, an international private equity investment and advisory firm, based in Hong Kong.
By Tim Plaehn: Two weeks ago, I wrote that the government of Argentina was contemplating a takeover of the former national oil company YPF SA (YPF).
By Michael Terry:Over the last few months, shares of YPF Sociedad Anonima (YPF) have been getting taken to the woodshed over political rumblings regarding potential nationalization (in the last week, the beatings have accelerated).Sunday we read (on Bloomberg) that:
Bullfax.com - Market News & Analysis 2008-2011 Contact Us | About Us | Terms & Conditions


text:
Mon-Fri 4am-10pm PST Sat-Sun 5am-8pm PSTLive Chat
Mon-Fri 4am-10pm PST Sat-Sun 5am-8pm PST
Save on all Keystone Fabrics products
return to topLearn more about Keystone Fabrics
Hardware is the best place to shop for Keystone Fabrics products
Keystone Fabric excels at providing top quality sunshades. Their sunshades help keep your indoor and outdoor living spaces comfortable by blocking the sun before it heats up your space. Their shades also reduce glare on your T.V. and reduces the fading of furniture and carpet. Their sunshades are also energy efficient by blocking out the sun in the summer keeping it cool and trapping in warmth in the winter keeping it warm. All of this translates into lower energy bills.
Related Products