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Old Jun 2, 2009, 6:11 AM   #1
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Default Shelf life of Li primary (throwaway) batteries

Long post follows, but there's not much happening in this forum otherwise, and it is quite an important issue.

I have given my 80-year-old mother-in-law (who lives down the road), my son's old & unused Sanyo S4 4Mpix camera, and she's been doing very well with it. It takes 2 AA cells.

However, it's been voraciously eating alkaline AAs, so I gave her my four AA 'Hybrio' low-self-discharge Ni-MH cells. In a fit of annoyance when these gave quite short life, she binned two of them, forgetting they were rechargeable. So now I've bought her a pack of four Li throwaway AAs, which I confidently expect to give her lots of shots.

Appalled at the cost, I did a price survey in our nearest town to find the cheapest outlet. I also priced throwaway CRV3 batteries, which also work the camera, but cost more than 2xAA Li. While I was at it, I also priced 'rechargeable CR-V3' Li-ion batteries and chargers, which I use myself in my own cameras.

My favoured cheap outlet, the local camera shop, didn't have any AA primary Li batteries, and maintained that they were difficult to source at present. He also said that he understood they had been unsuccessful from the point of view of the manufacturers, who had had difficulties with them, due to short shelf life. He did have CRV3 batteries. He thought that they were not just a pair of AAs in a different casing.

I just inspected the two old throwaway CRV3 cells I own, and measured their voltage and current delivered through the 37 ohm resistor of my 'battery test' DVM.

I was using one to maintain the settings in the stored one of my two Kodak superzoom cameras, while the other was in everyday use. To my horror, I found that it wouldn't turn the camera on, though it could still deliver a substantial current, and had successfully maintained all the camera settings. It had a date stamp of June 2009, so it's failed right on cue. That one is definitely newer than the other...

The other one, dated "01-2016" was used until exhausted back in June 2007, when I measured and wrote on it its voltage and current delivery. Remarkably, these values have changed little in the intervening 2 years, and I think it would still successfully work to keep the settings in the unused camera.

So my question to this esteemed community are...

1. Do primary lithium batteries have a short shelf life?

2. Are the alleged manufacturers' difficulties with primary Li AA real?

3. Are CR-V3 batteries just two AAs in a case?

4. How do other folk maintain the settings during storage on their occasionally-used cameras?

5. What has happened to the excellent and knowledgeable gentleman 'SilverFoxCPF',who used to post knowledgeably in this forum, and was, according to his profile, a 'battery tester' by profession?

6. Are there any other real battery experts around here, from within the industry? I was myself an alleged 'battery expert' in an electricity research establishment, but what we need here is a real expert.

Any thoughts welcome.
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Old Jun 2, 2009, 8:48 PM   #2
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I won't claim to be a 'real expert', but have picked up bits of knowledge here and there.
Primary Li cells, as used in watch batteries, etc., have a cell voltage of 3v, and shelf life of 5-10 years ( as claimed by mfr,though I have seen some in service a memory backup which are approaching 15years).
Lithium AA cells must have something added to reduce the cell voltage, and this may reduce shelf life and possibly service life as well. (though the Energizers I have on hand have use by dates of 10 years in future) ((will have to wait and see))
Haven't disassembled CR-V3 to look at, but it would be my guess that it would be simpler to make a 3v single cell, than to put together two AAs. (cheaper to make, and sell for more - who would do it the other way?)
My Minolta D7hi which only sees occasional service now, was manufactured in 2003 and still maintains settings, even though I store it without batteries. I did get the CCD replaced last year, and the service facility may have replaced the internal cell, though it wasn't noted on the service report.
One could probably find much of this information on the web. I occasionally try this, but, still being on dial-up, I find waiting for pages to load too time consuming unless the information is vital.

brian
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Old Jun 3, 2009, 3:11 AM   #3
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Quote:
Originally Posted by VTphotog View Post
...One could probably find much of this information on the web....
You're right Brian, and Wikipedia does indeed have a very good article....

http://en.wikipedia.org/wiki/Lithium_batteries

You've tactfully reminded me to read it and do my homework properly, thanks! However, it doesn't address my specific questions about whether there's a manufacturing issue of some kind.

Quote:
...Primary Li cells, as used in watch batteries, etc., have a cell voltage of 3v, and shelf life of 5-10 years .....Lithium AA cells must have something added to reduce the cell voltage, and this may reduce shelf life and possibly service life as well.
The Wikipedia article says 'Energizer Li' use iron sulphides as cathodes in organic solvents, which give the right voltage range (about 1.5) because of the chemistry, so no reduction is necessary. Reduction is necessary in rechargeable Li-ion CRV3 batteries intended for 2xAA 3V cameras, in case the native 3.8-4.2V of that chemistry inflicts damaging overvoltage. [Li-ion batteries aren't lithium batteries at all; the lithium ions are just current carriers in the reversible oxidation of transition metals salts.]

Quote:
...my guess that it would be simpler to make a 3v single cell, than to put together two AAs. .........
Yes, but that would have to be one of the other, 3V, different, chemistries. So if you're right, 2xLi AA and CR-V3 could well be different animals altogether.

As you say, we'll have to wait & see. I'll keep a diary of mother-in-law's photography & battery use - I back up all her shots anyway.

Last edited by Alan T; Jun 3, 2009 at 4:06 AM.
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Old Jun 3, 2009, 11:35 AM   #4
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Wow! Never had any idea there were as many different chemistries for Lithium primary cells.

My observations are at best limited but this is a case history of one set of Kodak branded AA li primary cells. I purchased a pair of these cells ( about $10) in ~1995 and put them in an AA powered electric razor which I use when I travel. Over the next 10 years I used that razor about one week a year and the razor showed no signs of slowing down until the eleventh year. In a couple of other razors of this type alkyline AAs are good for about a month in six days a week usage.

I purchased two Kodak CV-R3 at the same time I purchased my Z612. One these remains seal in it's package. The other I used for about 60 shots last June at an airshow and then again for about 12 shot last Jan. The battery indicater did not even show up in Jan. (indicating lots of life left). I'll measure the voltage under a test load tonight and edit this post.

A. C.

A. C.

Last edited by ac.smith; Jun 3, 2009 at 11:38 AM.
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Old Jun 4, 2009, 12:17 PM   #5
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1. The shelf life of Lithium AA primaries are incredible. I pulled some AA Li cells out of cold storage after sitting for a year and they registered with 100% remaining capacity.

2. I've not read anything about this.

3.Pretty much, you can use 2 AA batteries in digicams that take a CRV3 cell.

4. I use eneloop cells for all my cams that take AA cells. When it's time to top them off, I just put full eneloop cells in the cam while they're charging, then swap them back out.

5. Silverfox is around, mostly at CPF. Haven't seen him post here for a bit.

No doubt about it, Li AA/AAA cells are going to run a lot more than alkalines. I use li AA/AAA cells in my flashlights, but not my cameras. For my cameras, I use eneloop cells, which are more durable than the Hybrio cells you mentioned. They hold their charge and voltage longer.

For my cameras that use AA cells, I store them with eneloops. When they need to be topped off, I swap them with charged eneloops, charge the cells, then swap them back. If it has a backup battery, the settings will be preserved during the battery change.

Li primaries are the cells of choice for low temperatures and have low self discharge rates. I use them in my flashlights for a couple reasons: 1. I don't use my lights all that often, so their low self-discharge allows me to "grab 'n go" after they've been sitting. I could use eneloop cells for the low self discharge but . . .2. They're brighter when using Li AA vs. Alkaline or NiMH cells. This because of the 1.5V rating of the Li cells. Granted it's not leaps and bounds brighter, enough for me to use them and finally 3. I'm more likely to use my lights outside in the winter.

I could carry a set of Li AAs with my cams for emergency backup, but I have fully charged/tested eneloops for that same purpose.

A family member was buying CRV3 cells for her camera and paying the exorbanent prices. I suggested she look into eneloop (4-Pack of re-chargable eneloop cells are about the same as a single CRV3) and she's been using eneloop ever since.
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Old Jun 4, 2009, 8:39 PM   #6
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I have a CR123A cell which is 25 years old that still reads 3v no load. I bought it as a spare for something I no longer own so it has just been sitting on the shelf. The memory retention cell in my 18 year-old satellite receiver still holds program info during power outages.

I modified a 2AA flashlight (torch, for the UK crowd) to use high intensity LED, and found that alkalines would just make it light up, but very low brightness. It takes 3v just to forward bias the diode, leaving little to create current to make light. The higher cell voltage of the lithium AAs gives me a very bright, long lasting light I know is going to operate when I need it.

brian

Edit: Also should mention that I have tried out my Minolta d7hi with the Lithium AAs, and noticed that they get really warm in operation, similar to some NiMH cells I had which weren't intended for high drain use. Makes me think the internal resistance may be a bit higher than I have been led to believe.

Another edit: I have depleted a CR-V3 Kodak primary battery, and in the interests of accuracy, disassembled it, to find that it is indeed, two AA size cells wired together with a plasic case. For this to make economic sense, it must be that the chemistry is sefficiently cheaper than the 3V lithiums.

Last edited by VTphotog; Mar 12, 2010 at 9:31 PM. Reason: update info
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Old Jun 4, 2009, 10:16 PM   #7
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"One these remains seal in it's package. The other I used for about 60 shots last June at an airshow and then again for about 12 shot last Jan. The battery indicater did not even show up in Jan. (indicating lots of life left). I'll measure the voltage under a test load tonight and edit this post."


As promised I've measured the two CR-V3 I purchased DEC 2006. The one I've used for about 60 shots shows an open circuit voltage of 3.1 VDC and will punch 8.6 mA though a 375 ohm resistor. The battery is marked with an expiration date of July 2015. My unused CR-V3, which until now was in its unopened factory packaging, measured 3.17 VDC and pushed 8.7 mA through a 375 ohm load. The expiration date is May 2016.

Yes I know the math shows that they had a higher voltage into load than the open circuit voltage. Welcome to the real world.

Final note, while most cameras that take AA batteries work fine on NiMH AAs the Kodak Z*12 cameras do not. They want Li cells, either primary or re-chargeable.

A. C.

Last edited by ac.smith; Jun 5, 2009 at 9:58 AM.
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Old Jun 5, 2009, 4:04 AM   #8
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Thanks, everybody. It sounds as though Li primaries should last well, and that's what I thought before hearing the scare story. I am reassured, not wanting any more mother-in-law battery trouble, but disappointed to have been fed a red herring of a story.

When I got my Z712 in May 07, I used a primary Kodak CRV3 for hundreds of shots, before I got my rechargeables. I still have it, dated 01-2016. In Jun 2007 it had failed in the camera, but measured...

2.83V on o/c, and delivered 59.5mA through 37 ohms.
Now, 2 years later, it's 2.86V and delivers 51mA.
(Did you mean 86 and 87mA, A. C., rather than 8.5 and 8.6mA ? Or 375 ohms?)


I've had another primary Duracell CRV3, dated "06/09", backing up my Z1012 while not in use. I thought, probably wrongly, that it was little used. It started the camera successfully a few weeks ago, but day before yesterday it wouldn't. That now has 2.91V o/c, and delivers 62.7mA.

I conclude that although both these won't actually start the cameras, they still have a good bit of metallic lithium and cathode reactant present, and will continue to work as non-operational backup batteries.

For comparison, with the 37 ohm resistor, my two rechargeable CR-V3s show 3.75V o/c, 92mA, and 3.81V o/c, 91.5mA, both recharged some time ago. The KLIC-8000 in current use is 3.84V, 105mA.

Thanks again. Sorry if I alarmed anybody!
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Old Jun 5, 2009, 9:53 AM   #9
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(Did you mean 86 and 87mA, A. C., rather than 8.5 and 8.6mA ? Or 375 ohms?)

Ah! The floating decimal point. 375 Ohms would be the correct number.

Thanks.

A. C.
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Old Jun 9, 2009, 12:56 AM   #10
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Hello Alan,

There are a few brands of Lithium primary cells around. Some of them are less expensive, and also have had some problems. The Energizer cells have performed very well, and I would recommend them over the others.

The AA size Energizer L91 cell is listed to have a 15 year shelf life at room temperature, after which it has at least 90% of its initial capacity. This is a pretty long storage life.

The CRV3 batteries have a 10 year shelf life. There are a few varieties of these as well, but I am not up on all of the configurations.

Tom
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