Non-mutually exclusive classification sum of probabilities
You are correct: a probability cannot be larger than 1.

At the final layer, the activations (also known as logits), are passed through the final a softmax function in order to fulfill this constraint. The standard neural network does not have an implicit mechanism by it can ensure that constraint is met during training etc.



By non-mutual classification, we could be talking about something like classifying cat and dog images - in which case the label for each image either cat or dog. So they are mutually exclusive. This is a very common case - almost any form of image classification falls into this category.

You do not use a sigmomid function (or any other non-linearity for that matter) after the final layer, as there are no neurons following them, making a non-linearity somewhat redundant. Using a non-linearity for the purpose of fitting a non-linear model is different to the purpose of a final softmax function. This has exactly the purpose of scaling the final logits/activations into the nice range of [0, 1] that can be interpreted as probabilities. That allows us to make simple rules on how to classify the outputs - e.g. if p = [0.51, 0.49] then that sample was a cat, whereas p =[0.49, 0.51] is a dog.

I used those values in the example to highlight a further point; namely that you cannot interpret them as pure probabilities. Those examples don't mean the model was really unsure in both cases because all four "probabilities" we close to 0.5. The model gives more weight to the option is believes is correct - the relative magnitudes of those values are not directly interpretable.