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I have a lot of different devices that are powered with batteries such as CR2032, CR2450N, CR3032... All of them are marked as 3V but they have different mAH values.

The local shops don't always have the appropriate battery so I have to purchase them online which I don't fancy doing. Can I use similar batteries as long as they are Lithium 3V and of equal size?

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CR2032, CR2450N, CR3032 are different sizes. That is the only difference.

CR2032:
C - Lithium.
R - Round.
20 - Millimeter diameter.
3(.)2 - Millimeters high -- note the implicit decimal point!

The size determines the amount of material it can fit, larger cell has a larger capacity.

You could try if an CR2025 fits your device, some holders can handle more sizes.

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    \$\begingroup\$ Note the height is in 0.1mm steps so CR2032 is 3.2mm (not 32) high. \$\endgroup\$ – user_1818839 Sep 9 '17 at 12:49

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