IIRC, electricity is used to activate the release of neurotransmitters (intercellular communication is actually chemical, not electrical); the more interesting things are what governs the activation potential, the weights of the inputs and the connections between neurons. assuming that you can modify the activation potential across an axon, you still won't change the relative weights of its inputs or the neuron's connections...
The distinction is that generally we think of "electricity" as a cascade of electrons, whereas action potentials are a cascade of ions. The net effect of both is a transfer of charge, but the mechanism is slightly different.
it's definitely an electro-chemical gradient of sorts. at the cellular junction i believe the messages being transmitted are mostly receptor based (neurotransmitters) but there possibly some external ionic messages as well. I believe what you're referring to is when an action potential of ionic charge moves up a neuron and triggers the release of neurotransmitters. The message inside the neuron is due to the behavior of ions, and the message externally by receptor-binding neurotransmitters.
