CN112216815A - Lithium manganese battery positive electrode and lithium manganese battery - Google Patents
Lithium manganese battery positive electrode and lithium manganese battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
The invention relates to the field of lithium-manganese batteries, and discloses a lithium-manganese battery anode and a lithium-manganese battery. The lithium manganese battery positive electrode includes: a positive current collector, a positive active material, a conductive agent and a binder; wherein the positive electrode active material includes manganese dioxide and lithium carbonate. A lithium manganese battery is provided which may not employ lithium metal as a negative electrode. The cost of the lithium manganese battery can be reduced, and the safety is improved. And the assembly of electric core can be carried out in ordinary environment for it is more convenient to operate.
Description
Technical Field
The invention relates to the field of lithium-manganese batteries, in particular to a lithium-manganese battery anode and a lithium-manganese battery.
Background
Lithium manganese battery, called lithium-manganese dioxide battery (Li-MnO)2) Positive electrode activity thereofManganese dioxide is used as the material. Since manganese dioxide does not contain lithium, the negative electrode of the battery must be a lithium-containing material. Lithium metal is commonly used as the negative electrode of lithium manganese batteries as the lithium source for the battery. However, lithium metal is adopted as the negative electrode, on one hand, the price of the lithium metal is high, the cost of the battery is high, on the other hand, the lithium of the negative electrode is excessive, and the lithium is too active, so that potential safety hazards exist in the lithium manganese battery.
Disclosure of Invention
The invention aims to solve the problem of potential safety hazard of a lithium-manganese battery, and provides a lithium-manganese battery anode and a lithium-manganese battery.
In order to achieve the above object, a first aspect of the present invention provides a lithium manganese battery positive electrode comprising: a positive current collector, a positive active material, a conductive agent and a binder; wherein the positive electrode active material comprises manganese dioxide and lithium carbonate (Li)2CO3)。
Preferably, the lithium carbonate is contained in an amount of 30 to 50 wt% based on the total amount of the positive electrode active material.
Preferably, the manganese dioxide has a particle size of 200nm to 20 μm.
Preferably, the lithium carbonate has a particle size of 50nm to 20 μm.
Preferably, the mass ratio of the positive electrode active material, the conductive agent and the binder is (80-95): (3-10): (2-10).
A second aspect of the present invention provides a lithium manganese battery comprising: the invention relates to a lithium-manganese battery anode, a lithium-manganese battery cathode, a diaphragm and electrolyte.
Preferably, the lithium manganese battery negative electrode includes: the negative electrode comprises a negative electrode current collector, a negative electrode active material, a binder and an optional conductive agent, wherein the negative electrode active material is selected from one or more of graphite, silicon oxide and silicon carbide.
Preferably, the mass ratio of the negative electrode active material, the conductive agent and the binder (90-98): (0-5): (2-5).
Preferably, the electrolyte contains a lithium salt and a nonaqueous solvent.
Preferably, in the electrolyte, the concentration of the lithium salt is 0.1-5 mol/L.
Through the technical scheme, the invention provides the lithium-manganese battery which does not adopt lithium metal as a negative electrode. The cost of the lithium manganese battery can be reduced, and the safety performance of the battery can be improved. And lithium metal is not used, and the assembly of the battery cell can be carried out in a common environment, so that the operation is more convenient. According to the lithium manganese battery provided by the invention, the positive electrode contains lithium carbonate which can be used as a lithium source for working of the battery, so that a negative electrode can adopt a substance which does not contain lithium, such as graphite, the use of a metal lithium negative electrode can be avoided, and the safety performance of the battery is greatly improved. In addition, when the lithium manganese battery provided by the invention works, the lithium manganese battery needs to be charged firstly, so that lithium carbonate in the positive electrode is decomposed and removed to obtain lithium ions in the battery cycle, and further, the negative electrode active material embeds lithium; during discharging, the negative electrode active material is subjected to lithium removal, the manganese dioxide in the positive electrode is subjected to lithium intercalation, and in the subsequent battery cycle, lithium ions are removed between the positive electrode manganese dioxide and the negative electrode active material, so that the normal battery cycle performance is maintained.
Drawings
FIG. 1 is a first charge and discharge curve of a battery S10 produced in an example of the present invention and a first discharge curve of a DS10 produced in a comparative example.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides, in a first aspect, a lithium manganese battery positive electrode comprising: a positive current collector, a positive active material, a conductive agent and a binder; wherein the positive electrode active material includes manganese dioxide and lithium carbonate.
The inventor of the invention finds that in the research process, the design of the positive electrode and the negative electrode of the lithium-manganese battery is improved, manganese dioxide in the composition of the positive electrode of the lithium-manganese battery is used as an active substance capable of inserting and extracting lithium, lithium carbonate is used as a lithium source of the battery, and lithium required in the battery circulation is provided, so that the lithium-manganese battery which does not adopt lithium metal as the negative electrode can be combined, and the safety of the lithium-manganese battery is improved.
According to the present invention, the manganese dioxide in the positive electrode active material may be commercial manganese dioxide, but the particle size of manganese dioxide is controlled to ensure the function of manganese dioxide, i.e., lithium can be inserted into and extracted from manganese dioxide during battery cycle. Preferably, the particle size of the manganese dioxide is from 200nm to 20 μm, preferably from 2 to 10 μm. The too low particle size of the manganese dioxide affects the compacted density thereof, and the too high particle size tends to cause untimely intercalation of lithium ions during discharge, thereby causing accumulation of electrons from the negative electrode on the positive electrode, resulting in a drop in voltage of the positive electrode, i.e., so-called polarization during discharge. Polarization reduces the voltage plateau and reduces the energy density of the battery, resulting in premature termination of the discharge of the battery.
According to the present invention, in the positive electrode active material, the lithium carbonate can be advantageously used by controlling the particle size of the lithium carbonate, that is, the lithium carbonate can be decomposed to release lithium ions when the battery is charged for the first time, so as to provide lithium required for the battery cycle. Preferably, the particle size of lithium carbonate is 50nm-20 μm, preferably 100-500 nm. Too low a particle size of lithium carbonate affects the compacted density of the positive electrode, and too high a particle size causes partial loss of electrical contact in the decomposition process of lithium carbonate, resulting in polarization, so that lithium carbonate cannot be completely decomposed. On one hand, the first effect of the battery is reduced due to incomplete decomposition, and on the other hand, in the subsequent battery cycle, the lithium carbonate which is not decomposed is continuously decomposed, and although lithium ions can be provided, carbon dioxide is generated, so that the battery is inflated, and the safety problem is brought.
According to the present invention, the lithium carbonate content in the positive active material also affects the electrical properties of the lithium manganese battery of the present invention. Preferably, the lithium carbonate is contained in an amount of 30 to 50% by weight, preferably 35 to 40% by weight, based on the total amount of the positive electrode active material. In the positive active material, the content of lithium carbonate needs to be ensured in a reasonable range, so that the active lithium provided by the lithium carbonate to the negative electrode is slightly more excessive than the lithium-embeddable capacity of the manganese dioxide, and the capacity of the manganese dioxide can be fully exerted during discharging. In addition, considering that a part of active lithium is also consumed by the negative electrode SEI film formation, it is required that the capacity that lithium carbonate can provide in the positive electrode active material must be larger than the lithium intercalation capacity of manganese dioxide and the capacity that the negative electrode SEI film consumes, and therefore the content of lithium carbonate in the positive electrode active material cannot be less than 30% by weight. A lithium carbonate content of less than 30 wt.% means that less lithium can be provided, while at the same time the content of manganese dioxide increases and the demand for lithium from manganese dioxide increases. The lithium carbonate content of less than 30 wt% may make the lithium carbonate unable to meet the requirement of manganese dioxide, resulting in no lithium intercalation of part of the manganese dioxide, resulting in waste of materials and affecting the overall capacity of the battery. However, the content of lithium carbonate cannot be too high, and when the content of lithium carbonate is higher than 50 wt%, and the manganese dioxide of the positive electrode is fully intercalated with lithium, a large amount of excessive lithium can be still remained in the negative electrode without intercalation, so that not only is the waste of lithium caused and the overall capacity of the battery is influenced, but also the potential safety hazard problem of the battery can be caused by excessive negative electrode active lithium.
In the present invention, the manganese dioxide and lithium carbonate included in the positive electrode active material may be added during preparation of the positive electrode slurry. Adding manganese dioxide, lithium carbonate, a conductive agent and a binder into a dispersing agent, and stirring to uniformly mix; or uniformly mixing manganese dioxide and lithium carbonate, and then adding the mixed material, the conductive agent and the binder into the dispersing agent to prepare the anode slurry. The mixing mode of the manganese dioxide and the lithium carbonate can be selected from grinding, ball milling and the like.
According to the present invention, it is preferable that the mass ratio of the positive electrode active material, the conductive agent, and the binder is (80-95): (3-10): (2-10). The content of the conductive agent and the binder is not easily too high, which may affect the energy density of the battery. Preferably (90-95): (3-5): (2-5)
In the present invention, the conductive agent is not limited, and may be at least one selected from acetylene black, carbon nanotubes, graphene, conductive carbon black, and conductive graphite; the binder is not limited and may be selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, polyethylene glycol, polyethylene oxide, epoxy resin, styrene-butadiene rubber, polymethyl cellulose sodium, hydroxypropyl methyl cellulose, and polypropylene alcohol.
In the invention, the positive current collector can be foamed nickel, stainless steel mesh or aluminum foil. When the lithium manganese battery is a button battery, the current collector can be made of foam nickel and stainless steel mesh, and can also be made of a positive electrode shell directly; when the lithium manganese battery is in a lamination mode, a winding mode and the like, the current collector is preferably an aluminum foil.
In the present invention, the lithium manganese battery positive electrode may be prepared by the following method.
For example, the positive electrode active material, the conductive agent and the binder are uniformly mixed and then added into the dispersant, and the mixture is uniformly stirred to form slurry A; and coating the slurry A on an aluminum foil, and drying to obtain the lithium-manganese battery anode.
Or, drying the slurry A, grinding the dried slurry A into powder, and tabletting the powder and the foamed nickel under certain pressure to obtain the lithium-manganese battery anode.
Or, drying the slurry A, grinding the dried slurry A into powder, and directly tabletting the powder under certain pressure to obtain the lithium-manganese battery anode.
In the present invention, the dispersant is selected from one or more of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethylsulfoxide, tetrahydrofuran and ethanol. Preferably, the mass ratio of (positive electrode active material, conductive agent, and binder) to the dispersant is 100: 50-1000, preferably 100: 50-100 parts of; more preferably 100: 50.
a second aspect of the present invention provides a lithium manganese battery comprising: the invention relates to a lithium-manganese battery anode, a lithium-manganese battery cathode, a diaphragm and electrolyte.
According to the present invention, preferably, the lithium manganese battery negative electrode includes: the negative electrode comprises a negative electrode current collector, a negative electrode active material, a conductive agent and a binder, wherein the negative electrode active material is selected from one or more of graphite, silicon oxide and silicon carbide. The negative electrode may not employ lithium metal. Graphite is preferred.
In the invention, the negative current collector can be foamed nickel, stainless steel mesh or copper foil. When the lithium manganese battery is a button battery, the current collector can be made of foam nickel and stainless steel mesh (the negative electrode can also be used), or the current collector can be made of the negative electrode shell directly; when the lithium manganese battery is in a lamination mode, a winding mode or the like, the current collector is preferably a copper foil.
In the present invention, the conductive agent included in the negative electrode of the lithium manganese battery is not limited, and may be at least one selected from the group consisting of acetylene black, carbon nanotubes, graphene, conductive carbon black, and conductive graphite. When the negative electrode active material is graphite, the negative electrode may not be selected with a conductive agent due to high conductivity of graphite. The binder is not limited and may be selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, polyethylene glycol, polyethylene oxide, epoxy resin, styrene-butadiene rubber, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, and polyallyl alcohol.
According to the present invention, it is preferable that the mass ratio of the negative electrode active material, the conductive agent, and the binder (90 to 98): (0-5): (2-5), preferably (95-98): (0-3): (2-3). The content of the conductive agent and the binder is not easily too high, which may affect the energy density of the battery.
In the present invention, the lithium manganese battery negative electrode may be prepared by the following method.
For example, the negative electrode active material, the conductive agent and the binder are uniformly mixed and then added to the dispersant, and the mixture is uniformly stirred to form slurry B; and coating the slurry B on copper foil, and drying to obtain the lithium-manganese battery cathode.
Or, drying the slurry B, grinding the dried slurry B into powder, and tabletting the powder and the foamed nickel under certain pressure to obtain the lithium-manganese battery cathode.
Or, drying the slurry B, grinding the dried slurry B into powder, and directly tabletting under certain pressure to obtain the lithium-manganese battery cathode.
In the present invention, the dispersant used in the preparation of the lithium manganese battery may be selected from one or more of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethylsulfoxide, tetrahydrofuran, water, and ethanol. Preferably, the mass ratio of (negative electrode active material, conductive agent, and binder) and the dispersant is 100: 50-1000, preferably 100: 50-100.
In the present invention, the separator may be selected from various separators used in lithium ion batteries well known to those skilled in the art, such as polyolefin microporous membrane (PP), polyethylene felt (PE), glass fiber felt or ultrafine glass fiber paper or PP/PE/PP. In a preferred embodiment, the separator is PP/PE/PP.
According to the present invention, preferably, the electrolytic solution contains a lithium salt and a nonaqueous solvent. The lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride and lithium iodide, and preferably potassium perchlorate; the non-aqueous solvent is selected from one or more of tetrahydrofuran, ethylene glycol dimethyl ether, gamma-butyrolactone, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, diethyl carbonate, dipropyl carbonate, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, N-dimethyl formamide, sulfolane, dimethyl sulfoxide, dimethyl sulfite and cyclic organic ester containing fluorine, sulfur or unsaturated bonds, preferably the combination of ethylene glycol dimethyl ether and propylene carbonate, and preferably the weight ratio of the ethylene glycol dimethyl ether to the propylene carbonate is 0.5-2: 1.
According to the present invention, preferably, the concentration of the lithium salt in the electrolyte is 0.1 to 5mol/L, preferably 0.5 to 2mol/L, and particularly preferably 1 mol/L.
The lithium manganese battery provided by the invention can also comprise a battery shell. The battery case is not limited in the present invention, and various battery cases known to those skilled in the art, such as a hard case, e.g., a steel case or an aluminum case, or a soft case, e.g., an aluminum-plastic film, may be used, and the shape and size may be designed according to actual situations. It should be noted that the lithium manganese battery of the present invention needs to be charged first, and the battery is in an incompletely sealed state during charging, so that the gas generated during charging can be discharged. And after the charging is finished, completely sealing the battery to obtain the finished product of the lithium-manganese battery.
The lithium manganese battery provided by the invention has the advantages of lower cost, more convenient operation and higher safety. Compared with the traditional lithium manganese battery used as a primary battery, the lithium manganese battery provided by the invention can be repeatedly used as a secondary battery, and is more energy-saving and environment-friendly.
The present invention will be described in detail below by way of examples.
Example 1
(1) Positive electrode
60 parts by weight of MnO2Powder (particle size 2 μm) and 40 parts by weight of Li2CO3Putting the powder (with the particle size of 200nm) into a stirring ball mill, adding ethanol to obtain 50 wt% of solid content, carrying out wet mixing and grinding for 1h at a ball-to-material ratio of 5:1, putting the obtained slurry into a 60 ℃ oven for drying, and obtaining MnO2-Li2CO3Material, labeled S1.
S1 is used as a positive electrode material, acetylene black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, N-methylpyrrolidone (NMP) is used as a dispersing agent, and the mass ratio of the positive electrode material to the negative electrode material is as follows: acetylene black: PVDF: NMP 95:3:2: uniformly mixing the components in a ratio of 50, coating the mixture on an aluminum foil, then placing the aluminum foil in a 120 ℃ oven for vacuum drying for 24 hours, tabletting, and rolling and cutting to prepare a positive plate P1;
(2) negative electrode
Uniformly mixing graphite, styrene butadiene rubber, sodium carboxymethylcellulose and water according to a mass ratio of 95:3:2:50, coating on a copper foil, then placing in an oven at 80 ℃ for vacuum drying for 24 hours, tabletting, and rolling and cutting to prepare a negative plate;
(3) lithium manganese cell
1mol/L LiClO by taking celgard2400 polypropylene porous membrane as a separator4The mixed solution (volume ratio is 1:1) of ethylene glycol dimethyl ether and propylene carbonate is used as electrolyte; the assembly of the test cell was completed in a glove box filled with argon, the positive electrode sheet P1, the separator and the negative electrode sheet were wound into a cell and put into a square cell case, and the initial cell S10' was produced by mounting a lid plate and injecting the electrolyte without blocking the injection hole.
The initial cell S10' is in an incompletely sealed state. And charging the initial battery S10' in the glove box, adding the electrolyte after the charging is finished, and finally sealing the liquid injection hole to obtain a battery sample S10.
Example 2
65 parts by weight of MnO2Powder (particle size 5 μm) and 35 parts by weight of Li2CO3Putting the powder (with the particle size of 100nm) into a stirring ball mill, adding ethanol to obtain a mixture with the solid content of 60 wt% and the ball-to-material ratio of 5:1, carrying out wet mixing and grinding for 1h, putting the obtained slurry into a 60 ℃ oven, and drying to obtain MnO2-Li2CO3Material, labeled S2.
Referring to the method of example 1, a positive electrode sheet P2, a negative electrode sheet and a battery sample S20 were manufactured using S2 as a positive electrode material.
Example 3
MnO of2Powder (particle size 2 μm), Li2CO3Powder (particle size 200nm), acetylene black, PVDF and NMP were mixed according to 54: 36: 5: 5: 50 mass ratio, and coating on aluminum foil (wherein MnO is2Powder and Li2CO3The powder is formed into MnO according to a proportion2-Li2CO3Material marked as S3), then placing the material in an oven at 120 ℃ for vacuum drying for 24h, then tabletting and rolling cutting to prepare the positive plate P3.
A negative electrode sheet was produced by referring to the methods of steps (2) and (3) in example 1, and then a battery sample S30 was prepared. Wherein the cathode material is S3.
Comparative example 1
In MnO2Powder (particle size 2 μm) as a positive electrode active material was mixed with acetylene black, PVDF and NMP in a ratio of 95:3:2:50, preparing a positive plate; the negative plate is a lithium foil;
1mol/L LiClO by taking celgard2400 polypropylene porous membrane as a separator4The mixed solution (volume ratio is 1:1) of ethylene glycol dimethyl ether and propylene carbonate is used as electrolyte; and (3) completing the assembly of the test battery in a glove box filled with argon, winding the positive plate, the diaphragm and the negative plate into a battery core, putting the battery core into a square battery shell, installing a cover plate, injecting electrolyte, and completely sealing after the first injection, wherein the obtained initial battery is the final battery sample DS 10.
Example 4
Reference was made to the procedure of example 2 to produce cell sample DS20, except that Li2CO3The particle size of the powder was 30 μm.
Example 5
Referring to the method of example 3, a battery sample DS30 was prepared, except that MnO was added2Powder and Li2CO3The mass ratio of the powder to the acetylene black to the PVDF to the NMP is 30: 60: 5: 5: 50.
test example
1. Specific capacity of charge and discharge
The specific charge and discharge capacity of the batteries prepared in the examples and the comparative examples was measured on a charge and discharge tester. The results are shown in Table 1 and FIG. 1.
Setting the initial battery to be in a charging state, namely, removing lithium from the working electrode, charging the initial battery to a cut-off voltage of 4.4V, namely, stopping the operation, and calculating the first charging specific capacity.
First lithium removal specific capacity (mAh/g) is equal to first lithium removal capacity/mass of manganese dioxide in active substance
And after the first lithium removal is finished, completely sealing the battery, setting the battery to be in a discharge state, namely embedding lithium into the working electrode, wherein the discharge current is 20mA, and the discharge is finished when the discharge is finished to the cut-off voltage of 2V, and calculating the first discharge specific capacity.
First lithium intercalation specific capacity (mAh/g) being first lithium intercalation capacity/mass of manganese dioxide in the active material
For cell sample DS10, it was not charged, but only discharged.
Fig. 1 shows a charge/discharge curve of battery sample S10 and a discharge curve of DS10 at a charge/discharge rate of 0.05C. It can be found that the first specific charge capacity of S10 is 466.8mAh/g, and the first specific discharge capacity is 250.3 mAh/g; the specific first discharge capacity of the DS10 is 251.4 mAh/g. The first discharge specific capacities of the batteries S10 and DS10 are very close, which shows that the negative electrode of S10 can provide enough active lithium to the manganese dioxide of the positive electrode, and also shows that lithium carbonate serving as a lithium source is added to the positive electrode and can replace a metal lithium source of the negative electrode.
TABLE 1
In DS20 cell, Li with particle size of 30 μm is used2CO3The charging specific capacity is only 303.4mAh/g, which is 19.7 percent lower than S20, the specific capacity during discharging is also reduced by 15.1 percent, and only 213.2mAh/g, and the result shows that the lithium carbonate with large particle size cannot be completely decomposed and cannot provide sufficient active lithium for the negative electrode.
In the DS30 battery, the content of manganese dioxide is too low, the content of lithium carbonate is too high, and although the discharge specific capacity of the battery is normal, a large amount of active lithium still remains in the negative electrode and cannot be inserted into the positive electrode, so that a large amount of active lithium is wasted, and the battery has serious potential safety hazard.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A lithium manganese battery positive electrode comprising: a positive current collector, a positive active material, a conductive agent and a binder; wherein the positive electrode active material includes manganese dioxide and lithium carbonate.
2. The positive electrode for a lithium manganese battery according to claim 1, wherein the particle size of manganese dioxide is 200nm to 20 μm, preferably 2 to 10 μm.
3. The lithium manganese battery positive electrode according to claim 1 or 2, wherein the particle size of lithium carbonate is 50nm-20 μm, preferably 100-500 nm.
4. The positive electrode for a lithium manganese battery according to any one of claims 1 to 3, wherein lithium carbonate is contained in an amount of 30 to 50% by weight, preferably 35 to 40% by weight, based on the total amount of the positive electrode active material.
5. The lithium manganese battery positive electrode according to any one of claims 1 to 4, wherein the mass ratio of the positive electrode active material, the conductive agent and the binder is (80-95): (3-10): (2-10), preferably (90-95): (3-5): (2-5).
6. A lithium manganese battery comprising: the positive electrode for lithium manganese battery, the negative electrode for lithium manganese battery, the separator, the electrolyte according to any one of claims 1 to 5.
7. The lithium manganese battery of claim 6 wherein the lithium manganese battery negative electrode comprises: the negative electrode comprises a negative electrode current collector, a negative electrode active material, a binder and an optional conductive agent, wherein the negative electrode active material is selected from one or more of graphite, silicon oxide and silicon carbide.
8. The lithium manganese battery according to claim 7, wherein the mass ratio of the negative active material, the conductive agent and the binder (90-98): (0-5): (2-5), preferably (95-98): (0-3): (2-3).
9. The lithium manganese battery according to any one of claims 6 to 7, wherein the electrolyte contains a lithium salt and a non-aqueous solvent;
the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride and lithium iodide;
the non-aqueous solvent is selected from one or more of tetrahydrofuran, ethylene glycol dimethyl ether, gamma-butyrolactone, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, diethyl carbonate, dipropyl carbonate, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, N-dimethyl formamide, sulfolane, dimethyl sulfoxide, dimethyl sulfite and cyclic organic ester containing fluorine, sulfur or unsaturated bonds.
10. The lithium manganese battery according to claim 9, wherein the concentration of the lithium salt in the electrolyte is 0.1-5mol/L, preferably 0.5-2 mol/L.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446180A (en) * | 2000-07-10 | 2003-10-01 | 吉莱特公司 | Mechanochemical synthesis of lithiated manganese dioxide |
| CN1538541A (en) * | 2003-07-15 | 2004-10-20 | 新乡无氧铜材总厂 | Preparation technology of lithium manganese oxide positive electrode material for lithium ion battery |
| CN1633394A (en) * | 2002-02-21 | 2005-06-29 | 东曹株式会社 | Lithium-manganese composite oxide granular secondary particle, method for production thereof and use thereof |
| EP1305645B1 (en) * | 2000-07-29 | 2005-07-27 | Newson Gale Limited | Electrical resistance monitoring device |
| CN1853293A (en) * | 2003-08-27 | 2006-10-25 | 吉莱特公司 | Cathode material and method of manufacturing |
| CN101209859A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | λ－MnO 2 Preparation method of (2) |
| CN101279768A (en) * | 2008-05-30 | 2008-10-08 | 汪以道 | Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery |
| CN102637849A (en) * | 2012-05-04 | 2012-08-15 | 上海锦众信息科技有限公司 | Preparation method of coating cathode material of lithium ion battery |
| CN104681816A (en) * | 2013-11-28 | 2015-06-03 | 河南科隆新能源有限公司 | Lithium-manganese-oxide-based positive electrode active material and preparation method thereof |
| CN106784808A (en) * | 2015-11-20 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | A kind of single-phase positive electrode, its preparation method and lithium ion battery |
| DE102016208407A1 (en) * | 2016-05-17 | 2017-11-23 | Technische Universität Bergakademie Freiberg | Process for the recovery of lithium carbonate from lithium-containing battery residues by means of CO2 treatment |
-
2019
- 2019-07-11 CN CN201910626347.XA patent/CN112216815B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446180A (en) * | 2000-07-10 | 2003-10-01 | 吉莱特公司 | Mechanochemical synthesis of lithiated manganese dioxide |
| EP1305645B1 (en) * | 2000-07-29 | 2005-07-27 | Newson Gale Limited | Electrical resistance monitoring device |
| CN1633394A (en) * | 2002-02-21 | 2005-06-29 | 东曹株式会社 | Lithium-manganese composite oxide granular secondary particle, method for production thereof and use thereof |
| CN1538541A (en) * | 2003-07-15 | 2004-10-20 | 新乡无氧铜材总厂 | Preparation technology of lithium manganese oxide positive electrode material for lithium ion battery |
| CN1853293A (en) * | 2003-08-27 | 2006-10-25 | 吉莱特公司 | Cathode material and method of manufacturing |
| CN101209859A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | λ－MnO 2 Preparation method of (2) |
| CN101279768A (en) * | 2008-05-30 | 2008-10-08 | 汪以道 | Hybridization method of lithium salt and electrolytic manganese dioxide, application thereof to lithium battery |
| CN102637849A (en) * | 2012-05-04 | 2012-08-15 | 上海锦众信息科技有限公司 | Preparation method of coating cathode material of lithium ion battery |
| CN104681816A (en) * | 2013-11-28 | 2015-06-03 | 河南科隆新能源有限公司 | Lithium-manganese-oxide-based positive electrode active material and preparation method thereof |
| CN106784808A (en) * | 2015-11-20 | 2017-05-31 | 中国科学院宁波材料技术与工程研究所 | A kind of single-phase positive electrode, its preparation method and lithium ion battery |
| DE102016208407A1 (en) * | 2016-05-17 | 2017-11-23 | Technische Universität Bergakademie Freiberg | Process for the recovery of lithium carbonate from lithium-containing battery residues by means of CO2 treatment |
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