CN107331878B - Pore-forming agent for lithium-manganese dioxide battery positive electrode, porous positive electrode prepared from pore-forming agent and lithium-manganese dioxide battery - Google Patents
Pore-forming agent for lithium-manganese dioxide battery positive electrode, porous positive electrode prepared from pore-forming agent and lithium-manganese dioxide battery Download PDFInfo
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- CN107331878B CN107331878B CN201710399170.5A CN201710399170A CN107331878B CN 107331878 B CN107331878 B CN 107331878B CN 201710399170 A CN201710399170 A CN 201710399170A CN 107331878 B CN107331878 B CN 107331878B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
Abstract
The invention discloses a pore-forming agent for a lithium-manganese dioxide battery anode, a porous anode prepared by the pore-forming agent and a lithium-manganese dioxide battery. The pore-forming agent is any one or a combination of at least two of fatty acid polyoxyethylene esters, fatty alcohol polyoxyethylene ethers and isomers thereof, and polyoxyethylene ethers with the relative molecular weight of 200-750. According to the invention, by adding a proper kind of pore-forming agent, adjusting the addition amount of the pore-forming agent and drying at a proper temperature, a porous anode with proper pores can be prepared, and the liquid absorption performance of the anode is improved while the anode has good strength, so that the high-current discharge performance of the lithium-manganese dioxide battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium primary batteries, and relates to a pore-forming agent for a lithium-manganese dioxide battery anode, a porous anode prepared by adopting the pore-forming agent and a lithium-manganese dioxide battery.
Background
The lithium primary battery is one of the series with the highest specific energy in the known chemical power series, and the lithium-manganese dioxide primary battery (lithium manganese battery for short) is the safest one of the series, and is the lithium primary battery with the highest output, the highest output value and the most extensive application at present. Lithium manganese batteries are widely used in memories and backup power supplies, various smart meters, wireless alarms/sensors, remote monitoring systems, automotive electronics, electronic toll collection systems, and even military equipment.
The positive electrode of a lithium manganese battery generally consists of an active material, manganese dioxide, a conductive agent and a binder. The material forms a film through external mechanical pressure and adheres to a current collector, and the pole piece has higher compaction density, but has the defect of poor liquid absorption capacity of the pole piece, so that the ion conduction capacity of the positive pole in the discharging process is poor, and the pressure drop of the battery in the discharging process is increased.
The positive electrode is used as a core part of the lithium manganese battery, the electrochemical performance of the lithium manganese battery is directly influenced by the performance of the positive electrode, and certain research is carried out on the positive electrode in order to improve the performance of the lithium manganese battery.
CN106450339A discloses a positive plate of a lithium manganese battery, which includes a positive plate current collector and a positive active material coated on the positive plate current collector. The positive plate current collector is made of iron alloy foil, so that more positive active materials can be coated, and higher pressure can be borne in a rolling process, so that the capacity of the battery is improved. There are problems that the liquid-absorbing ability of the positive electrode sheet cannot be improved and the large-current discharge ability of such a battery cannot be improved.
CN104124428A discloses a coiling formula lithium manganese cell positive plate, its active layer upper surface is provided with the netted groove of intercommunication each other, has groove structure on the positive plate, compares the smooth positive plate of tradition, has increased the storage space of electrolyte. Although the scheme improves the holding capacity of the electrolyte and improves the discharge efficiency of the battery, the scheme has the problems of complicated manufacturing process and higher cost.
In order to improve the liquid absorption capacity of the electrode plate, the preparation of the porous electrode is one of feasible ways, but in the preparation process, the unreasonable pore-forming way can cause the problems of severe expansion and reduction of rate capability and cycle performance of the battery in the use process.
Pore formers are additives that increase the pore structure in the material, and are generally materials that readily decompose into gases. In the existing technology for preparing the lithium ion battery, a diaphragm is prepared by adding a 1- (2-pyridylazo) -2-naphthol pore-forming agent into diaphragm slurry, so that the property of the diaphragm can be improved and the performance of the battery can be improved, but the diaphragm exists in a non-solvent state generally, so that the viscosity of the slurry is reduced, and although the method can improve the electrochemical performance of the lithium ion battery, the improvement effect is limited, and the lithium ion battery is a secondary battery, and the diaphragm pore-forming technology is not suitable for being applied to the preparation of the anode of the lithium manganese battery.
CN103165877A discloses a method for preparing a negative electrode material of a lithium titanate battery, in which a pore-forming technique is used, and titanium hydroxide powder or metatitanic acid powder, a pore-forming agent and water are used to obtain mesoporous spherical titanium dioxide powder. And doping and clamping a lithium precursor and a carbon precursor into the holes of the mesoporous material, and co-firing to obtain the lithium titanate powder material. By carrying out internal doping filling or external wrapping on micropores of the mesoporous spherical titanium dioxide, the close contact among small particles in spherical particles is enhanced, the conductivity is increased, the mass transfer resistance is reduced, and the high-rate performance is enhanced. Although the document discloses a pore-forming technology of a pore-forming agent and can enhance the performance of high rate, the proposal firstly uses the pore-forming agent to prepare titanium dioxide which is a precursor of a negative electrode material with mesoporous morphology, then doping a lithium precursor and a carbon precursor to prepare the lithium titanate battery cathode material, wherein the principle is that by enhancing the internal contact tightness among small particles in spherical particles, the product performance is improved by pertinently improving the structure of the lithium titanate cathode by changing the structure of the titanium source in the lithium titanate, but because the titanium source is used for different types of batteries, the preparation method of the negative electrode is different (for example, for the lithium ion battery, the electrode preparation needs to coat the electrode slurry on the current collector to obtain the electrode, while the electrode of the primary battery does not need the coating process and presses and bonds the electrode wet ball onto the current collector to obtain the electrode), and the negative electrode material is not suitable for other electrodes or other types of batteries.
Therefore, development of simple and inexpensive improvement technology applicable to the positive electrode of lithium manganese batteries to improve the liquid absorption performance of the positive electrode of such batteries has been the focus of research in the field.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a pore-forming agent for a positive electrode of a lithium-manganese dioxide battery, a porous positive electrode prepared by using the pore-forming agent, and a lithium-manganese dioxide battery. According to the invention, the porous anode with appropriate pores is prepared by adopting the specific pore-forming agent, so that the liquid absorption performance of the anode is improved, and the anode has good strength, thereby improving the high-current discharge performance of the lithium-manganese dioxide battery.
In a first aspect, the invention provides a pore-forming agent for a lithium-manganese dioxide battery anode, wherein the pore-forming agent is any one or a combination of at least two of fatty acid polyoxyethylene esters, fatty alcohol polyoxyethylene ethers and isomers thereof, and polyoxyethylene ethers with the relative molecular weight of 200-750.
In the present invention, the fatty acid polyoxyethylene esters having a relative molecular weight of 200 to 750 have a relative molecular weight of, for example, 200, 300, 350, 400, 500, 600, 650, 700, or 750.
Preferably, the polyoxyethylene fatty acid ester with the relative molecular weight of 200-750 comprises one or a combination of two of polyethylene glycol oleate and polyoxyethylene abietate.
Preferably, the polyoxyethylene ether includes any one of trideceth-8, octylphenyl polyoxyethylene ether, or isooctyl polyoxyethylene ether, or a combination of at least two thereof, preferably trideceth-8.
Preferably, the fatty alcohol polyoxyethylene ether and isomers thereof include any one of or a combination of at least two of laurinol polyoxyethylene ether, isomeric octal polyoxyethylene ether and isomeric undecanol polyoxyethylene ether.
The pore-forming agent disclosed by the invention has the following characteristics: 1) the lithium-manganese dioxide battery cathode material has two parts of a hydrophilic group and a hydrophobic group, so that on one hand, the lithium-manganese dioxide battery cathode material is easy to dissolve in water, and can be uniformly mixed in the anode material of the lithium-manganese dioxide battery; on the other hand, the emulsion has a certain dispersion effect on the binder emulsion, and can help the binder and manganese dioxide, conductive carbon black and other powder materials to be uniformly dispersed; 2) the porous anode has proper thermal decomposition temperature, so that the pore-forming agent is effectively removed while the components and the structures of the anode active substance, the binder, the conductive carbon black and the like are not damaged, and the porous anode is prepared.
As the preferable technical scheme of the pore-forming agent for the lithium-manganese dioxide battery anode, the pore-forming agent is polyoxyethylene ether, and by adopting the pore-forming agent, on one hand, the dispersibility of manganese dioxide, a binder and conductive carbon black can be improved; on the other hand, the porous positive electrode with proper pores can be prepared after the drying step is removed, so that the liquid absorption performance of the positive electrode is improved, and the large-current discharge capacity of the battery is greatly improved.
In a second aspect, the present invention provides a positive electrode material, wherein the positive electrode material comprises the pore-forming agent of the first aspect.
As a preferable technical scheme of the lithium-manganese dioxide cathode material, the cathode material comprises manganese dioxide, conductive carbon black, a binder and a pore-forming agent.
Preferably, the conductive carbon black includes acetylene black, graphite and ketjen black, but is not limited to the above-listed conductive carbon blacks, and other conductive carbon blacks commonly used in the art may also be used in the present invention.
Preferably, the binder is a fluoropolymer.
Preferably, the binder includes any one or a combination of at least two of Polytetrafluoroethylene (PTFE) and/or polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (NaCMC), or Styrene Butadiene Rubber (SBR), preferably Polytetrafluoroethylene.
In a preferred embodiment of the positive electrode material for a lithium-manganese dioxide battery of the present invention, the manganese dioxide is 85 wt% to 95 wt%, for example, 85 wt%, 87 wt%, 88 wt%, 90 wt%, 92.5 wt%, 93.5 wt%, or 95 wt%, based on 100 wt% of the total mass of the manganese dioxide, the conductive carbon black, and the binder.
Preferably, the conductive carbon black is present in a mass percent of 0.5 wt% to 5 wt%, such as 0.5 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.25 wt%, 2.6 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, etc., based on 100 wt% of the total mass of manganese dioxide, conductive carbon black, and binder.
Preferably, the binder is present in a mass percentage of 1 wt% to 8 wt%, such as 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 4.5 wt%, 5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 8 wt%, or the like, based on 100 wt% of the total mass of the manganese dioxide, the conductive carbon black, and the binder.
Preferably, the pore-forming agent is contained in an amount of 0.5 wt% to 3 wt%, for example, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.2 wt%, 2.6 wt%, 2.8 wt%, 3 wt%, etc., based on 100 wt% of the total mass of the manganese dioxide, the conductive carbon black and the binder. The mass percentage of the pore-forming agent is limited to 0.5-3 wt%, so that the porous anode prepared by the pore-forming agent has proper pores, and the large-current discharge performance of the battery is improved while the liquid absorption amount is properly increased; if the mass percentage of the pore-forming agent is less than 0.5 wt%, the pore-forming effect is not obvious, and the liquid absorption capacity of the anode is influenced; if the mass percentage of the pore-forming agent is higher than 3 wt%, the liquid absorption amount of the porous anode prepared by the pore-forming agent is too large, so that the anode expands in the discharging process, the contact between the anode plate and the current collector and the anode active material is influenced, and the discharging performance of the battery is influenced.
In a third aspect, the present invention provides a porous positive electrode for a lithium-manganese dioxide battery obtained by granulating the positive electrode material for a lithium-manganese dioxide battery according to claim 4, pressing the granules into a sheet, and drying the sheet.
The drying step after the pressing into the tablet can remove the pore-forming agent, so that the pore-forming of the positive electrode is realized, and the porous positive electrode of the lithium-manganese dioxide battery is obtained.
Preferably, the granulating process comprises: and fully mixing manganese dioxide, a conductive carbon black binder and a pore-forming agent, and granulating.
Preferably, the apparatus used for tableting is a tableting machine.
Preferably, the temperature of the drying is 160 ℃ to 300 ℃, such as 160 ℃, 175 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃ and the like.
According to the invention, the drying temperature is selected to be suitable for the pore-forming agent, in the drying process, the pore-forming agent reaches the decomposition temperature and is decomposed and volatilized, so that the pore-forming function is achieved, the porous anode is prepared, the liquid absorption amount of the anode is increased, the reaction interface is increased, the polarization is reduced, and the performance of the battery is improved. The more preferable temperature for the baking is 180 to 300 c, for example 180 c, 200 c, 220 c, 280 c or 300 c, but not limited to the recited values, and other values not recited in the above range are also applicable, and in the preferable range of 180 to 300 c, the pore-forming agent is decomposed and removed to prepare the porous positive electrode, and the excellent functions of the active component, the binder, the conductive agent, and the like of the porous positive electrode are ensured, and the porous positive electrode has appropriate strength.
In a fourth aspect, the present invention provides a lithium-manganese dioxide battery comprising a lithium-manganese dioxide battery porous positive electrode as described in the third aspect.
Preferably, the lithium-manganese dioxide battery is prepared by the following steps: the button CR2032 battery is assembled by the porous positive electrode, the negative electrode (metal lithium or lithium aluminum alloy), the polypropylene diaphragm and the electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a pore-forming agent for a lithium-manganese dioxide battery anode, which can be used for preparing a porous anode with proper pores by adding a proper type of pore-forming agent, adjusting the addition amount of the pore-forming agent and drying at a proper temperature, improves the liquid absorption performance of the anode and has good strength, thereby having excellent high-current discharge performance.
Drawings
Fig. 1 is a graph showing the results of 1K Ω discharge performance test of lithium-manganese dioxide batteries of examples 1 to 6 and comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Comparative example 1
(1) Stirring 89 wt% of MnO2, 5 wt% of Ketjen black and 6 wt% of polytetrafluoroethylene by taking the total mass of manganese dioxide, conductive carbon black and a binder as 100 wt%, fully mixing, granulating, tabletting to prepare CR2032 positive plates, placing the positive plates in an oven at 200 ℃ for baking for 12 hours, and (2) assembling the positive electrode obtained in the step (1), negative electrode metal lithium, an electrolyte (ethylene glycol dimethyl ether of 1 mol/L lithium perchlorate and propylene carbonate solution) and a diaphragm into a lithium-manganese dioxide battery.
Example 1
(1) Based on the total mass of the manganese dioxide, the conductive carbon black and the binder as 100 weight percent, adding 89 weight percent of MnO2Mixing with 5 wt% of Ketjen black, 6 wt% of polytetrafluoroethylene and 1 wt% of tridecyl polyoxyethylene (8) ether, granulating by stirring, tabletting to obtain CR2032 positive electrode sheets, wherein the weight of each positive electrode sheet is 0.93-1.00g, baking in an oven at 200 ℃ for 12h, and decomposing and removing tridecyl polyoxyethylene (8) ether to obtain the porous positive electrode.
(2) And (2) assembling the porous anode obtained in the step (1), the metal lithium of the cathode, an electrolyte (1 mol/L ethylene glycol dimethyl ether of lithium perchlorate and propylene carbonate solution) and a diaphragm into a lithium-manganese dioxide battery.
Example 2
The preparation method and conditions were the same as in example 1 except that 1 wt% of trideceth-8 was replaced with 1 wt% of polyethylene glycol oleate.
Embodiment 3
The preparation method and conditions were the same as in example 1 except that 1 wt% of trideceth-8 was replaced with 1 wt% of isomeric octal polyoxyethylene ether.
Example 4
(1) Based on the total mass of the manganese dioxide, the conductive carbon black and the binder as 100 wt%, 91.5 wt% of MnO2Fully mixing with 3.5 wt% of acetylene black, 5 wt% of polytetrafluoroethylene and 1.5 wt% of tridecyl polyoxyethylene (8) ether, granulating, tabletting to obtain CR2032 positive plates, wherein the weight of each positive plate is 0.93-1.00g, baking at 280 ℃ in an oven for 6h, and decomposing and removing the tridecyl polyoxyethylene (8) ether to obtain the porous positive electrode.
(2) And (2) assembling the porous anode obtained in the step (1), the metal lithium of the cathode, an electrolyte (1 mol/L ethylene glycol dimethyl ether of lithium perchlorate and propylene carbonate solution) and a diaphragm into a lithium-manganese dioxide battery.
Example 5
(1) Taking the total mass of manganese dioxide, conductive carbon black and a binder as 100 wt%, adding 87 wt% of MnO2Fully mixing the powder with 5 wt% of Ketjen black, 8 wt% of polyvinylidene fluoride and 3 wt% of tridecyl polyoxyethylene (8) ether by stirring, granulating, tabletting to obtain CR2032 positive plates, wherein the weight of each positive plate is 0.93-1.00g, baking in an oven at 260 ℃ for 10h, and decomposing and removing the tridecyl polyoxyethylene (8) ether to obtain the porous positive electrode.
(2) And (2) assembling the porous anode obtained in the step (1), the metal lithium of the cathode, an electrolyte (1 mol/L ethylene glycol dimethyl ether of lithium perchlorate and propylene carbonate solution) and a diaphragm into a lithium-manganese dioxide battery.
Example 6
(1) Based on the total mass of the manganese dioxide, the conductive carbon black and the binder as 100 wt%, the MnO content is 90 wt%2Fully mixing the graphite with 3.5 wt% of graphite, 6.5 wt% of sodium hydroxy cellulose and 0.5 wt% of tridecyl polyoxyethylene (8) ether, granulating, tabletting to obtain CR2032 positive plates, wherein the weight of each positive plate is 0.93-1.00g, baking in an oven at 300 ℃ for 5h, and decomposing and removing the tridecyl polyoxyethylene (8) ether to obtain the porous positive electrode.
(2) And (2) assembling the porous anode obtained in the step (1), the metal lithium of the cathode, an electrolyte (1 mol/L ethylene glycol dimethyl ether of lithium perchlorate and propylene carbonate solution) and a diaphragm into a lithium-manganese dioxide battery.
The porous positive electrodes of examples 1 to 6 and the positive electrode of comparative example 1 were measured for the amount of liquid absorbed, and the amount of liquid absorbed (g) was the weight after the positive electrode had absorbed liquid to the weight before the positive electrode had absorbed liquid. The test results are shown in table 1, and it can be seen that the liquid absorption of the lithium-manganese dioxide porous electrode prepared using the pore-forming agent of the present invention is significantly increased relative to comparative example 1.
TABLE 1
The 1K omega discharge performance of the lithium-manganese dioxide batteries of examples 1-6 and comparative example 1 is detected, and the test result is shown in fig. 1, which shows that the 1K omega discharge platform of the lithium-manganese dioxide porous electrode assembled by the lithium battery prepared by using the pore-forming agent of the invention is improved, and the lithium battery of example 4 has the best discharge performance; on the other hand, although the liquid absorption amount of the porous positive electrode of example 5 is higher than that of example 4, and the discharge performance is inferior to that of example 4, since the amount of the positive electrode liquid absorption is the best due to the larger amount of the added liquid of example 5, the positive electrode swells during the discharge process due to the larger amount of the absorbed electrolyte, and the contact between the electrode sheet and the current collector and the positive electrode active material is affected, thereby affecting the discharge performance of the battery.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (13)
1. The porous positive electrode of the lithium-manganese dioxide battery is characterized in that the positive electrode of the lithium-manganese dioxide battery is obtained by granulating a positive electrode material of the lithium-manganese dioxide battery, pressing the granules into tablets and drying the tablets, wherein the drying temperature is 160-300 ℃;
the lithium-manganese dioxide battery positive electrode material comprises manganese dioxide, conductive carbon black, a binder and a pore-forming agent, wherein the total mass of the manganese dioxide, the conductive carbon black and the binder is 100 wt%, the mass percentage of the pore-forming agent is 0.5-3 wt%, and the pore-forming agent is any one or a combination of at least two of tridecyl polyoxyethylene (8) ether, octyl phenyl polyoxyethylene ether or isooctyl polyoxyethylene ether.
2. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the pore former is trideceth-8.
3. The lithium-manganese dioxide battery porous positive electrode according to claim 1, wherein the conductive carbon black includes acetylene black, graphite, and ketjen black.
4. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the binder is a fluoropolymer.
5. The porous positive electrode for a lithium-manganese dioxide battery according to claim 4, wherein the binder comprises any one of or a combination of at least two of polytetrafluoroethylene PTFE and/or polyvinylidene fluoride PVDF, sodium carboxymethylcellulose NaCMC or styrene butadiene rubber SBR.
6. The porous positive electrode for a lithium-manganese dioxide battery according to claim 5, wherein the binder is polytetrafluoroethylene.
7. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the mass percentage of manganese dioxide in the positive electrode material for a lithium-manganese dioxide battery is 85 to 95 wt% based on 100 wt% of the total mass of manganese dioxide, conductive carbon black and the binder.
8. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the conductive carbon black is contained in an amount of 0.5 to 5% by mass based on 100% by mass of the total mass of the manganese dioxide, the conductive carbon black and the binder.
9. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the binder is contained in an amount of 1 to 8% by mass based on 100% by mass of the total mass of the manganese dioxide, the conductive carbon black and the binder.
10. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the granulating comprises: and fully mixing manganese dioxide, a conductive carbon black binder and a pore-forming agent, and granulating.
11. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the apparatus for pressing into a sheet is a tablet machine.
12. The porous positive electrode for a lithium-manganese dioxide battery according to claim 1, wherein the temperature for drying is 180 ℃ to 300 ℃.
13. A lithium-manganese dioxide battery comprising the lithium-manganese dioxide battery porous positive electrode of claim 1.
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| CN112366321A (en) * | 2020-11-18 | 2021-02-12 | 惠州亿纬锂能股份有限公司 | Pole piece, preparation method thereof and battery comprising pole piece |
| CN112838188A (en) * | 2021-02-03 | 2021-05-25 | 常州宇峰电池有限公司 | Manufacturing method of storage-resistant lithium-manganese battery positive electrode |
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| US4328288A (en) * | 1980-07-25 | 1982-05-04 | Duracell International Inc. | Method for improving stability of Li/MnO2 cells |
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| CN102931378B (en) * | 2012-10-09 | 2016-01-20 | 东莞市创明电池技术有限公司 | Lithium ion cell electrode and preparation method thereof, lithium ion battery |
| CN106340679A (en) * | 2016-10-27 | 2017-01-18 | 惠州亿纬锂能股份有限公司 | Preparation method of lithium-manganese dioxide battery |
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