Any charger like a B2B, solar controller or mains charger will have diodes to prevent any unwanted back-feeding of current. They can be safely wired to the battery, and the one with the highest voltage does the charging job. The point about the split charge relay is that it is a direct metallic connection across the input and output of the B2B, effectively shorting it and therefore making it useless.
A B2B doesn't necessarily have a higher voltage than the alternator output, it just usually does. When the leisure battery is full, the B2B will drop into float mode, but the alternator might still be at 14.4V or more. When the starter battery is full, the alternator will reduce its output voltage, but if the leisure battery is not full the B2B will continue to charge at the optimum voltage. If the leisure battery is a different technology (Gel, AGM etc) the B2B can charge it correctly, independently of what the alternator does to the starter battery.
A B2B doesn't necessarily have a higher voltage than the alternator output, it just usually does. When the leisure battery is full, the B2B will drop into float mode, but the alternator might still be at 14.4V or more. When the starter battery is full, the alternator will reduce its output voltage, but if the leisure battery is not full the B2B will continue to charge at the optimum voltage. If the leisure battery is a different technology (Gel, AGM etc) the B2B can charge it correctly, independently of what the alternator does to the starter battery.