No. A separate CPF Submission Number (CSN) is required for voluntary contributions (VC) - the CSN for mandatory contributions should not be used for this purpose.
To make VC to your employee's three CPF accounts, use your existing CSN with the payment code "VCT" (eg. 123456789-VCT-01). To make Additional MediSave Contributions Scheme (AMCS) contributions to your employee's MediSave Account, use your existing CSN with the payment code "AMS" (eg. 123456789-AMS-01).
Submission and payment of VC for your employees can be done the same way as mandatory CPF contributions via CPF EZPay. If you do not have a CSN with the "VCT" or "AMS" payment code, you may
apply for one.