“Payment on Account” means that you pay tax in two instalments:
First in January (the usual deadline for paying the tax bill for last year), second in July.
In your first year as self-employed, you will likely have to pay 150% of your tax bill in one go.
For example: your tax bill for 2019/20 is £9,000. You need to pay this in full by January 31st 2021, but you also need to pay an additional advance payment of £4,500 (50% of £9,000) at the same time.
Finally, you have to pay another £4,500 by July 31st 2021.
Basically, it's an advance payment. If you turn out to earn less or more this tax year, HMRC will adjust it for you, and refund if needed.
Also, if you earn more than 80% of your income through PAYE, you won't need to use Payments on Account.