Expressing so he can "help" is a false economy IMO - you spend just as long washing, sterilising and of course expressing as you would have done feeding in the first place! Also, it can cause supply problems this early on. It can be helpful for some people, but it's not generally a good first resort.
Things he can do to help:
Change nappies, change clothes, change bedding
Make you food (from a cup of tea, to the evening meal, to making you stacks of sandwiches which you can eat during the day one-handed whilst feeding while he is at work)
Wind/settle the baby after a feed
General household tasks like washing, cleaning, washing up, etc. If you are behind on the washing could he take it ALL to the launderette and get it all done in one go so you are back to the beginning?
Look after the baby for an hour so you can sleep/get a hair cut/go for a walk etc. (Feed just before you leave, the baby will be absolutely fine for an hour or two)
Have a bath with the baby and do some baby massage afterwards - again this ought to buy you about an hour's free time to sleep, read a book, go on mumsnet... (This was my absolute favourite suggestion, actually, I made bathing DS' dad's "specific" job as breastfeeding was "my" job and he loved it, it was a really special time for them) This is also a good beginning point for a bedtime routine in the future, and Dad gets skin-to-skin time with the baby which has loads of advantages as breastfeeding does.
Take the baby for a walk in his pram or to the supermarket, again to give you some space. (And do some shopping!) Supermarkets are open 24 hours don't forget - if needs be, he would not be the only frazzled parent of a newborn wandering around at 9pm, or even 3am. 
Help with night feeds by bringing the baby to you, you feed lying down and barely awake, he waits until you are finished and then does the winding and resettling in cot bit. (If not already co-sleeping, which cuts out the need for anyone to get up!)