Hi Brian. Thank you for your question.
In general, P50s are absolutely legal and compliant. They carry the CE mark for the Pressure Equipment Directive, comply with BS EN 3-7 for the manufacture of portable fire extinguishers, and are certified by BSI so carry the globally recognised Kitemark. More information can be found here:
https://www.safelincs.co.uk/are-p50-service-free-extinguishers-legal/
However, your mention of these being fitted in 11 kV sub-stations could be an issue.
If they are installed in storage rooms, offices, or other similar locations, then there should be no issue - as long as they satisfy the fire risks present and are maintained per the manufacturer's instructions.
If they are installed for use on anything operating above 1,000 V, then they are not suitable for that. Portable extinguishers to BS EN 3-7 bearing the lightning bolt symbol are safe to use around live electrical equipment up to 1,000 V but should not be specified for anything above that; specialist solutions should be sought for such applications.
The facility should have a suitable suppression system in place to mitigate or tackle fires without relying on humans to do so with handheld units, depending on original design and subsequent Fire Risk Assessments conducted by competent persons with knowledge and experience with sub-stations and LV / HV equipment. CO2 extinguishers are likely the best to have installed supplementary to a suppression system to allow trained persons to tackle smaller fires in the vicinity, as it is the safest agent to use around live electricity, but that is purely a supposition on my part and may not be suitable in practice - I have found several resources online recommending their use in this situation, but it is not something covered by BS EN 3-7 for portable extinguishers.
Unless something has been specifically arranged and documented for the facility, with appropriately trained staff, the focus for anyone on site during a fire should be to escape, not to tackle the fire. Portable extinguishers are primarily there to aid escape where fire is blocking the escape route, and P50s (depending on the fire Class) would be fine for this purpose as long as they are not discharged near anything above 1,000 V.