CN1622372A - Mercury-free environment-friendly alkaline battery - Google Patents
Mercury-free environment-friendly alkaline battery Download PDFInfo
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- CN1622372A CN1622372A CN 200310108858 CN200310108858A CN1622372A CN 1622372 A CN1622372 A CN 1622372A CN 200310108858 CN200310108858 CN 200310108858 CN 200310108858 A CN200310108858 A CN 200310108858A CN 1622372 A CN1622372 A CN 1622372A
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Abstract
The invention discloses a mercury-free environment-friendly alkaline battery, wherein the anode of the battery is mercury-free manganese dioxide, graphite and calcium stearate, the cathode of the battery is zinc oxide powder and indium hydroxide, the electrolyte is potassium hydroxide, the cathode is added with a binder, the binder is a three-dimensional reticular polymer super absorbent resin, and In (OH) is inorganic indium hydroxide 3 The zinc powder can be deposited on the surfaces of zinc powder and a current collector, and has the functions of inhibiting hydrogen precipitation and inhibiting corrosion, small internal resistance, good shock resistance and increased discharge capacity. Compared with the prior art, the invention solves the problem of harm of mercury to the environment and simultaneously meets the requirement of long continuous discharge time of the alkaline battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to an alkaline battery, and especially relates to a mercury-free environment-friendly alkaline battery.
Background
In the early sixties and late fifties, ALKALINE zinc-manganese batteries (ALKALINE) were developed by the invention of a few western Europe countries such as the United states, the United kingdom, france and the like, thereby opening the era of energy upgrade and full utilization of raw materials of human disposable dry batteries. The development of the alkaline zinc-manganese battery greatly solves the power supply required by people in the field of household appliances, and meanwhile, the alkaline zinc-manganese battery is still a novel power supply which has the highest capacity, the longest storage period and high and low temperature resistance in the current world 1.5V dry batteries. The dry battery occupies 60 to 80 percent of the market demand of the whole dry battery in developed countries, and only occupies about 10 to 15 percent of the market demand in China at present. The alkaline zinc-manganese dioxide cell contains mercury, the mercury in the alkaline zinc-manganese dioxide cell mainly has the effects of improving the hydrogen evolution overpotential of the zinc surface and amalgamating impurities, so that the gas evolution quantity of a zinc anode is reduced, the mercury is liquid metal at normal temperature, the mercury on the surface of amalgam zinc powder still has the property of fluid, and when zinc powder particles indirectly contact with zinc powder and a negative current collector, a mercury bridge is formed to improve the contact performance of the two contacts, so that the internal resistance of a negative electrode area is reduced, the load discharge performance, the anti-seismic performance and the recovery capability after the shock are improved, and the stability of a paste zinc anode can be kept; the mercury can prevent InO from forming deposition on the zinc surface in the discharge process, reduce anode polarization, ensure that zinc can be further dissolved, and ensure that the paste zinc anode has smaller internal resistance under heavy-load discharge. However, it is known that alkaline mercury batteries have a fatal problem of environmental pollution, and as the demand of alkaline batteries increases, the harm thereof is becoming more and more obvious. Therefore, the development of mercury-free environment-friendly alkaline zinc-manganese dioxide batteries is very necessary.
Disclosure of Invention
The technical problems to be solved by the invention in the prior art are as follows: the alkaline zinc-manganese dioxide battery in the prior art contains mercury, and the mercury has the fatal problem of environmental pollution.
The invention provides a mercury-free environment-friendly alkaline battery which comprises a positive electrode, a negative electrode, an electrolyte and a container for accommodating the electrolyte, wherein the negative electrode contains indium hydroxide, specifically, the positive electrode contains mercury-free manganese dioxide, graphite and calcium stearate, and further specifically, the negative electrode also contains zinc powder and zinc oxide, the electrolyte preferably adopts potassium hydroxide, and specifically, the indium hydroxide is used as a corrosion inhibitor of zinc paste in the negative electrode of the battery.
Further, a binder is added into the negative electrode, the binder is a three-dimensional network polymer super absorbent resin, and specifically, the binder has the following structural formula:
wherein X is an alkali metal element including hydrogen.
In the battery of the present invention, inorganic indium hydroxide In (OH) 3 Can be deposited on the surfaces of zinc powder and a current collector, has the functions of inhibiting hydrogen precipitation and inhibiting corrosion, small internal resistance, good shock resistance and increased discharge capacity, but has no high mercury capacity.
The adhesive can accelerate the movement of ions and reduce the resistance, and the CMC adhesive used at present has poor dissolving property and larger resistance, thereby hindering the rapid movement of the ions. The inventor of the invention screens the domestic adhesive and adopts the domestic three-dimensional reticular polymer super absorbent resin, so that the production cost is greatly reduced, and the adhesive effect reaches the international standard. The preparation principle of the super absorbent resin is as follows:
conventional CMC binders do not help with ion movement and the cell storage time is short, however indium has a lower conductivity and bridging capacity than mercury, so once hydrogen inhibition is solved, the internal resistance must be solved, thus solving both the ballooning problem and the internal resistance problem. The invention adopts super absorbent resin with more than 150 meshes, and zinc oxide, zinc powder, potassium hydroxide and SAP resin are selected to synthesize the calamine cream for binding the frozen body. Therefore, the problem that the indium conductivity and bridging capacity are poorer than that of mercury is solved, the reaction of raw materials is complete, and the capacitance is increased. When the battery is analyzed, the wettability of the zinc paste is increased, the conductivity coefficient is increased, the internal resistance is reduced, and the high water-absorbing resin is bonded into a jelly shape through synthesis. No paste block exists, the surface of the zinc powder is not in an inclusion state, and the conductivity of the collector in the zinc paste is increased. The super absorbent resin can resist high temperature and low temperature, and the synthesized zinc paste is bonded into a frozen body, so that the liquid leakage rate is greatly reduced (the specific data are described in the embodiment).
Compared with the prior art, the invention solves the problem of environmental harm caused by mercury and meets the requirement of long continuous discharge time of the alkaline battery.
Drawings
Fig. 1 is a 10 omega continuous discharge curve diagram of a mercury-free environmentally friendly alkaline battery of the present invention.
Fig. 2 is a graph showing the change of current during the storage life of 5# alkaline zinc-manganese dioxide battery using SAP as a binder for a mercury-free environmentally friendly alkaline battery of the present invention.
FIG. 3 is a graph showing the current change during the storage life of a No. 5 alkaline zinc-manganese dioxide battery using CMC binder for a mercury-free environmentally friendly alkaline battery of the present invention.
Fig. 4 is a graph showing the variation of current during the storage life of 7# alkaline zinc-manganese dioxide battery using SAP as a binder for a mercury-free eco-friendly alkaline battery according to the present invention.
Fig. 5 is a current change curve diagram of the shelf life of 7# alkaline zinc-manganese dioxide battery using CMC binder for mercury-free environmentally friendly alkaline battery of the present invention.
The specific implementation mode is as follows:
example 1
The adhesive is prepared by partially neutralizing acrylic acid with alkali, and polymerizing into slightly crosslinked three-dimensional network polymer in the presence of a small amount of crosslinking agent, wherein the specific chemical reaction is as follows:
example 2
The invention discloses a test table of a mercury-free environment-friendly alkaline battery under high temperature and high humidity, which comprises the following steps: (the specific test method is a conventional test method in the prior art)
The specific implementation conditions are as follows: the temperature is 60 ℃, the relative humidity is 75 percent, and the time is 21 minutes;
| no. 5 mercury-free environment-friendly alkaline battery | No. 7 mercury-free environment-friendly alkaline battery | ||||||||
| Open circuit voltage (V) | Open circuit voltage (V) | ||||||||
| 1.580 | 1.581 | 1.582 | 1.582 | 1.583 | 1.585 | 1.585 | 1.586 | 1.586 | 1.583 |
| 1.585 | 1.586 | 1.588 | 1.59 | 1.582 | 1.586 | 1.585 | 1.586 | ||
| 10 omega discharge time (h) | 10 omega discharge time (h) | ||||||||
| 15.2 | 15.3 | 15.8 | 15.85 | 15.8 | 7.1 | 7.2 | 7.18 | 7.2 | 6.9 |
| 15.88 | 15.88 | 15.92 | 15.95 | 6.7 | 7.3 | 7.1 | 7.2 | ||
The data show that the invention has stable performance under high temperature and high humidity conditions.
Example 3
As shown in fig. 1, the 10 Ω continuous discharge curve of the mercury-free environment-friendly alkaline battery of the present invention adopts a conventional test method according to specific test steps, and the test data are shown in the following table:
| open circuit Press (V) | Charge of electricity Press (V) | Short circuit electricity Flow (A) | Time to each specific voltage value (h) | |||||
| 1.600 | 1.550 | 14.5 | 1.4V | 1.3V | 1.2V | 1.1V | 1.0V | 0.9V |
| 0.5 | 2.0 | 6.0 | 12.2 | 15.0 | 16.5 | |||
From the above data, it is shown that the cells of the present invention have a long continuous discharge time.
Example 4
The following table shows the voltage comparison of the binder SAP and CMC for mercury-free environment-friendly alkaline batteries of the invention: (method of measurement Using conventional method of measurement)
| Adhesive agent | Battery set | Date of manufacture | Open circuit voltage | Rate of decline (％) | |
| Initial period | After 100 days of storage | ||||
| SAP | No. 7 | 2000/12/28 | 1.606 | 1.600 | 0.37 |
| 2001/01/15 | 1.612 | 1.607 | 0.31 | ||
| 2001/02/26 | 1.615 | 1.609 | 0.37 | ||
| | 2000/12/28 | 1.610 | 1.605 | 0.31 | |
| 2001/01/15 | 1.615 | 1.609 | 0.37 | ||
| 2001/02/26 | 1.612 | 1.606 | 0.37 | ||
| CMC | No. 7 | 2000/12/28 | 1.600 | 1.593 | 0.43 |
| 2001/01/15 | 1.599 | 1.593 | 0.37 | ||
| 2001/02/26 | 1.595 | 1.589 | 0.38 | ||
| | 2000/12/28 | 1.605 | 1.599 | 0.37 | |
| 2001/01/15 | 1.606 | 1.599 | 0.43 | ||
| 2001/02/26 | 1.603 | 1.595 | 0.49 |
From the above data, it was shown that the voltage of the battery using SAP was decreased less after 100 days of storage than the battery using CMC.
Example 5
The following table shows the current comparison of the SAP and CMC binder for mercury-free environment-friendly alkaline batteries of the present invention: (method of measurement Using conventional method of measurement)
| Adhesive agent | Battery set | Date of manufacture | Open circuit current | Rate of decline (％) | |
| Initial period | After 100 days of storage | ||||
| SAP | No. 7 | 2000/12/29 | 10.15 | 9.55 | 5.9 |
| 2001/01/10 | 10.20 | 9.50 | 6.9 | ||
| 2001/02/05 | 10.50 | 9.85 | 6.2 | ||
| | 2000/12/29 | 15.00 | 14.00 | 6.6 | |
| 2001/01/10 | 15.01 | 14.01 | 6.7 | ||
| 2001/02/05 | 15.20 | 14.20 | 6.6 | ||
| CMC | No. 7 | 2000/12/29 | 9.50 | 8.80 | 7.36 |
| 2001/01/10 | 9.90 | 9.20 | 7.0 | ||
| 2001/02/05 | 9.20 | 8.50 | 7.6 | ||
| | 2000/12/29 | 14.20 | 13.00 | 8.5 | |
| 2001/01/10 | 14.60 | 13.50 | 7.53 | ||
| 2001/02/05 | 14.50 | 13.30 | 8.3 |
From the above data, it was shown that the decrease in current was lower in the cell using SAP than in the cell using CMC after 100 days of storage.
Example 6
As shown in fig. 2, fig. 3, fig. 4 and fig. 5, the current change curves of 5# and 7# alkaline zn-mn batteries using SAP and CMC binder for 100 hours of the mercury-free environment-friendly alkaline battery of the present invention are shown. As can be seen from the graph, the change in current was not large within 100 hours of storage of 5# and 7# alkaline zinc-manganese batteries using SAP and CMC binders.
Example 7
The invention relates to a drop test of a mercury-free environment-friendly alkaline battery, which comprises the following steps:
the dropping test is that the cement floor is dropped randomly at 2 m height, and the battery adopted in the test is No. 1 battery
| 1 | 2 | 3 | 4 | 5 | 6 | |||
| Original source Starting point | Open circuit voltage | 1.615 | 1.615 | 1.55 | 1.615 | 1.62 | 1.62 | |
| Load voltage | 1.59 | 1.585 | 1.50 | 1.58 | 1.58 | 1.585 | ||
| | 19 | 20 | 11 | 19.8 | 19.3 | 19 | ||
| First, the A Next time | Open circuit voltage | 1.6 | 1.61 | 1.53 | 1.61 | 1.61 | 1.61 | Is just for Pole(s) Upper part of |
| Load voltage | 1.57 | 1.58 | 1.50 | 1.58 | 1.58 | 1.57 | ||
| Electric current of | 19.3 | 20 | 9.8 | 19.2 | 17 | 15.8 | ||
| First, the II | Open circuit voltage | 1.6 | 1.60 | 1.53 | 1.60 | 1.60 | 1.60 | Negative pole Pole(s) |
| Load voltage | 1.58 | 1.58 | 1.50 | 1.58 | 1.58 | 1.58 |
| Then | Electric current of | 19 | 20 | 10.8 | 18 | 18 | 17.8 | On the upper part |
| First, the III Next time | Open circuit voltage | 1.59 | 1.60 | 1.51 | 1.58 | 1.59 | 1.59 | Cross bar |
| Load voltage | 1.18 | 1.58 | 1.50 | 1.58 | 1.57 | 1.57 | ||
| Electric current of | 19.8 | 19.6 | 8.6 | 18.8 | 17.2 | 16.3 | ||
| First, the Fourthly, the method Next time | Open circuit voltage | 1.59 | 1.59 | 1.53 | 1.59 | 1.60 | 1.59 | Is just Pole(s) On the upper part |
| Load voltage | 1.575 | 1.58 | 1.50 | 1.58 | 1.58 | 1.58 | ||
| | 17 | 18.8 | 9.5 | 17.6 | 17.5 | 15 | ||
| First, the Five of them Then | Open circuit voltage | 1.58 | 1.59 | 1.53 | 1.59 | 1.60 | 1.59 | |
| Load voltage | 1.57 | 1.58 | 1.50 | 1.56 | 1.57 | 1.57 | ||
| Electric current | 17.2 | 18.1 | 8.3 | 14.8 | 15 | 15.2 | ||
| First, the Six ingredients Next time | Open circuit voltage | 1.58 | 1.59 | 1.53 | 1.59 | 1.60 | 1.59 | Is just for Pole(s) Lower part |
| Load voltage | 1.57 | 1.58 | 1.50 | 1.56 | 1.57 | 1.57 | ||
| Electric current of | 17 | 19 | 9.8 | 14.3 | 13 | 14.1 | ||
| First, the Seven-piece Then | Open circuit voltage | 1.58 | 1.58 | 1.53 | 1.58 | 1.58 | 1.58 | Negative pole Pole(s) Lower part |
| Load voltage | 1.57 | 1.57 | 1.50 | 1.57 | 1.56 | 1.56 | ||
| Electric current | 16.1 | 17.3 | 8 | 14.8 | 11.8 | 15.2 | ||
| First, the Eight-part Next time | Open circuit voltage | 1.58 | 1.58 | 1.58 | 1.57 | 1.58 | 1.58 | Horizontal bar |
| Load voltage | 1.57 | 1.56 | 1.50 | 1.56 | 1.54 | 1.54 | ||
| Electric current | 15.6 | 18.6 | 6.3 | 12.8 | 9.2 | 14.2 | ||
| First, the Nine-piece Next time | Open circuit voltage | 1.58 | 1.58 | 1.58 | 1.58 | 1.57 | 1.58 | Is just Pole(s) Lower part |
| Load voltage | 1.55 | 1.56 | 1.49 | 1.55 | 1.55 | 1.57 | ||
| Electric current of | 13.3 | 17.2 | 6.8 | 10.2 | 9.2 | 12.1 | ||
| First, the Ten items Next time | Open circuit voltage | 1.57 | 1.53 | 1.53 | 1.57 | 1.57 | 1.57 | Negative pole Pole Lower part |
| Load voltage | 1.55 | 1.52 | 1.50 | 1.56 | 1.56 | 1.55 | ||
| Electric current of | 13.8 | 15.3 | 6.1 | 10.2 | 10.2 | 13.3 |
The discharge time of 1 Ω is as follows:
| | 1 | 2 | 3 | 4 | 5 | 6 |
| Discharge time (minutes) | 455 | 377 | 433 | 393 | 398 | 458 |
| Discharge time (hour) | 7.58 | 6.28 | 7.22 | 6.55 | 6.63 | 7.6 |
Tests show that three data of open-circuit voltage, load voltage and short-circuit current have no obvious rules, and after ten drops, six batteries have no short-circuit phenomenon, so that the battery has stable performance and long continuous effective discharge time.
Example 8 Process flow for preparing Environment-friendly alkaline cell
Spraying conductive graphite emulsion on the positive steel cylinder, and drying for later use; mixing electrolytic manganese dioxide, graphite, electrolyte and adhesive, tabletting and granulating, beating the anode ring, and then introducing the anode ring into the anode steel cylinder. The diaphragm casing is formed with diaphragm paper, coated with a sealing glue, and then injected with an electrolyte. Stirring electrolyte, zinc powder, adhesive (the material of the adhesive is the adhesive in example 1) and water to prepare zinc paste, and injecting the zinc paste into the cylinder; assembling a negative electrode by using a copper needle, a small sealing bowl, a sealing ring and a negative electrode cover, coating a sealing agent to prepare a collector electrode, and inserting the collector electrode into the cylinder. Then rolling, shaping and placing.
Claims (6)
1. The mercury-free environment-friendly alkaline battery consists of a positive electrode, a negative electrode, electrolyte and a container for containing the electrolyte, and is characterized in that: the negative electrode contains indium hydroxide.
2. The mercury-free environment-friendly alkaline battery as claimed in claim 1, wherein: the positive electrode contains mercury-free manganese dioxide, graphite and calcium stearate.
3. The mercury-free environment-friendly alkaline battery as claimed in claim 1, wherein: the negative electrode contains zinc powder and zinc oxide.
4. The mercury-free environment-friendly alkaline battery as claimed in claim 1, wherein: the cathode contains zinc paste, and the zinc paste adopts indium zinc hydroxide as a corrosion inhibitor.
5. The mercury-free environment-friendly alkaline battery as claimed in claim 1, wherein: the electrolyte is potassium hydroxide.
6. The mercury-free environment-friendly alkaline battery as claimed in claim 1, wherein: the negative electrode is added with a binder, the binder is a three-dimensional network polymer super absorbent resin, and the three-dimensional network polymer super absorbent resin has the following structural formula:
wherein X is an alkali metal element including hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108858 CN1622372A (en) | 2003-11-25 | 2003-11-25 | Mercury-free environment-friendly alkaline battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108858 CN1622372A (en) | 2003-11-25 | 2003-11-25 | Mercury-free environment-friendly alkaline battery |
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|---|---|
| CN1622372A true CN1622372A (en) | 2005-06-01 |
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| CN 200310108858 Pending CN1622372A (en) | 2003-11-25 | 2003-11-25 | Mercury-free environment-friendly alkaline battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100401561C (en) * | 2006-08-24 | 2008-07-09 | 广州市天球实业有限公司 | Non-mercury button cell negative zinc cream and its making method |
| CN107302096A (en) * | 2017-07-24 | 2017-10-27 | 横店集团东磁股份有限公司 | Low-internal-resistance alkaline zinc-manganese battery and preparation method thereof |
-
2003
- 2003-11-25 CN CN 200310108858 patent/CN1622372A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100401561C (en) * | 2006-08-24 | 2008-07-09 | 广州市天球实业有限公司 | Non-mercury button cell negative zinc cream and its making method |
| CN107302096A (en) * | 2017-07-24 | 2017-10-27 | 横店集团东磁股份有限公司 | Low-internal-resistance alkaline zinc-manganese battery and preparation method thereof |
| CN107302096B (en) * | 2017-07-24 | 2019-04-30 | 横店集团东磁股份有限公司 | Low-internal-resistance alkaline zinc-manganese battery and preparation method thereof |
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