The HE mini store, is a part of the central heating system, in it can be included in the already in place expansion vessel (recheck sized based on increased system capacity) and relief valve etc.
Assume ministore has an immersion, it could be heated by that, but will not take much energy depending on the volume.
To get the most out of it, you need to set your boiler up to do priority domestic hot water. Which isn't as straightforward with a combi, but can be done. Then you can blast the ministore with high temp (80 Deg) water to ensure you actually have endless DHW in winter and top as needed in summer. Your immersion will hold the temperature while idle, but on hot water draw, will not keep up especially if running on excess PV via a diverter. So get your tin hat ready "the blo@dy hot water cold again" moments with the other half.