CN108400320B - Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material - Google Patents
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention relates to a method for vulcanizing the surface of a spinel lithium nickel manganese oxide positive electrode material, which comprises the steps of dissolving soluble L i, Ni and Mn compounds in deionized water according to a molar ratio to obtain a mixed solution, adding a metal ion chelating agent to obtain a gel liquid, drying and grinding the gel liquid into powder, calcining the gel liquid to obtain lithium nickel manganese oxide positive electrode material powder, dispersing the powder into absolute ethyl alcohol, adding 3-aminopropyltriethoxysilane, washing and centrifugally separating after reaction, drying to obtain surface-activated lithium nickel manganese oxide positive electrode material powder, dispersing the positive electrode material powder and thioacetamide into absolute ethyl alcohol, adjusting the pH value to 7.5-8.5, washing and centrifugally separating after reaction, and sintering after drying to obtain the surface-vulcanized lithium nickel manganese oxide positive electrode material.
Description
The technical field is as follows:
the invention relates to a method for vulcanizing the surface of a spinel lithium nickel manganese oxide positive electrode material, belonging to the technical field of lithium ion battery material preparation.
Technical Field
The lithium ion battery is a new generation of practical rechargeable and dischargeable storage battery, has the advantages of high working voltage, high energy density, long cycle life, no memory effect, small self-discharge and the like, is widely applied to various fields such as portable electronic products, electric tools, new energy vehicles, military equipment, aerospace, energy storage power systems and the like, and is regarded as a high-tech product which has important significance for people's life, national economy and social development in the 21 st century. The vigorous development of the fields of electric vehicles, smart power grids and large-scale energy storage makes lithium ion batteries with high working voltage and high energy density gradually become research hotspots in the industry field. The electrochemical performance of the lithium ion battery mainly depends on the structures and the performances of the used electrode active materials and electrolyte materials, wherein the anode material of the lithium ion battery directly determines the performances of the battery, such as energy density, power density, service life, safety characteristic and the like, and is a key influence factor of the performance of the lithium ion battery.
The spinel type lithium nickel manganese oxide is a positive electrode material with a three-dimensional lithium ion channel, the reversible specific capacity is 146.7mAh/g, and the de-intercalation lithium voltage platform is 4.7V vs L i/L i+On the other hand, the lithium ion battery has a higher energy density, is considered to be one of the most competitive positive electrode materials in the next generation of high energy density/high power density lithium ion battery, and has attracted high attention and extensive research of vast researchers. However, under high lithium extraction voltage, the electrolyte is easy to decompose on the surface of the lithium nickel manganese oxide, so that the quantity of a conductive medium in the battery is reduced; meanwhile, Mn in lithium nickel manganese oxide3+Easily generate Mn by disproportionation reaction2+And Mn4+In which Mn is2+Easily dissolved in electrolyte, so that Mn in the lithium nickel manganese oxide3+The corrosion of hydrofluoric acid in electrolyte on the nickel lithium manganate can be relieved, the dissolution of manganese is inhibited, and the cycle performance of the battery is further improved0.5Mn1.5O4The capacity retention rate of the spinel anode material after 100 cycles on the particle surface and after surface modification is 92 percent, and the capacity retention rate of the material without surface modification is only 74.7 percent, Peng et al utilize tetraethoxysilane hydrolysis technology at L iNi0.5Mn1.5O4The surface of the particles is modified with silica, the capacity retention of the material after the modification of the silica is obviously improved, Peng et al L iNi by a simple ethanol solution method of tin tetrachloride0.5Mn1.5O4SnO with the mass fraction of 2 wt% is deposited on the surfaces of the particles2Under the condition of 2C current charge and discharge, the capacity retention rate of the battery after 500 cycles can reach 57%. Deng et al utilize sol-gelsMethod at L iNi0.5Mn1.5O4Particle surface L i2SiO3The capacity retention rate is remarkably improved when the (1-x) L iNi0.5Mn1.5O4·x Li2SiO3Middle L i2SiO3When the coating amount x is 0.10, the initial discharge specific capacity of the positive electrode material is as high as 150.3 mAh/g. Although a large number of experimental reports prove that the electrochemical performance of the lithium nickel manganese oxide cathode material is remarkably improved by surface modification, most of the reported surface modification methods have some defects, such as that a surface modification layer cannot be well deposited on the surface of the cathode material, and the adhesion force between the surface modification layer and the surface of the cathode material is not strong, which undoubtedly increases the interfacial resistance between the cathode materials and negatively affects the improvement of the electrochemical performance of the cathode material.
Disclosure of Invention
In order to solve the problems existing in the conventional process for modifying the surface of the lithium nickel manganese oxide positive electrode material, the invention provides a method for in-situ vulcanization on the surface of a spinel positive electrode material, which can uniformly modify the particle surface of the positive electrode material and enhance the adhesion acting force between a surface modification layer and the surface of the positive electrode material, so that the lithium nickel manganese oxide positive electrode material with high electrochemical performance is prepared.
The technical scheme adopted for realizing the purpose of the invention is as follows:
1. dissolving soluble L i, Ni and Mn compounds in deionized water according to the molar ratio of (1+ x) to 0.5:1.5, and fully stirring to obtain a clear mixed solution, wherein x is more than or equal to 0 and less than or equal to 0.1;
2. adding a metal ion chelating agent into the mixed solution, stirring for 6-10 hours, and then adjusting the pH value of the solution by using ammonia water or ethylenediamine, wherein the pH value range is 6-7.
3. And (3) placing the mixed solution obtained in the step (2) in a water bath kettle at the temperature of 80-90 ℃ to continue stirring and refluxing, and stirring for 8-24 hours to obtain gel liquid.
The soluble L i compound is one of lithium acetate, lithium nitrate and lithium sulfate.
The soluble Ni compound is one of nickel acetate, nickel nitrate and nickel sulfate.
The soluble Mn compound is one of manganese acetate, manganese nitrate and manganese sulfate.
The metal ion chelating agent is oxalic acid, citric acid or tartaric acid, and the dosage of the metal ion chelating agent is 2.0-4.0 times of the total molar weight of all metal ion substances in the mixed solution.
4. And (3) drying the gel liquid in an air atmosphere in an air blast drying oven or a muffle furnace, and then grinding the fluffy substance obtained after drying to obtain gel precursor powder. The drying temperature is a certain temperature within the range of 250-280 ℃, and the drying time is 8-24 hours.
5. And placing the collected gel precursor powder in a muffle furnace or an atmosphere furnace, calcining in two stages in the air or oxygen atmosphere, and cooling to room temperature along with the furnace after calcining is finished to obtain the lithium nickel manganese oxide cathode material.
The two-stage calcination comprises the following first stage: the calcination temperature is 450-550 ℃, the temperature rising rate from the room temperature to the calcination temperature is 1-5 ℃/min, and the calcination time is 3-8 hours; and a second stage: the calcination temperature is 850-950 ℃, the temperature rising rate from the first stage calcination temperature to the second stage calcination temperature is 2-5 ℃/min, and the calcination time is 9-20 hours.
6. Weighing a certain mass of lithium nickel manganese oxide positive electrode material, dispersing the positive electrode material in absolute ethyl alcohol, performing ultrasonic oscillation for 2-6 hours, and adding 3-aminopropyltriethoxysilane, wherein 0.03 g of lithium nickel manganese oxide needs 0.5-3 ml of 3-aminopropyltriethoxysilane. And after reacting for 5-15 hours, washing with absolute ethyl alcohol, performing centrifugal separation, and drying to obtain the surface-activated lithium nickel manganese oxide powder.
7. Weighing a certain mass of surface-activated lithium nickel manganese oxide powder and thioacetamide, dispersing in absolute ethyl alcohol, and then adjusting the pH value of the solution by using ammonia water or ethylenediamine, wherein the pH value range is 7.5-8.5. And after reacting for 3-6 hours, washing with absolute ethyl alcohol, performing centrifugal separation, and drying to obtain the lithium nickel manganese oxide powder with sulfur ions adsorbed on the surface.
8. Placing the lithium nickel manganese oxide powder with sulfur ions adsorbed on the surface in an atmosphere furnace, sintering in the atmosphere of argon or argon-hydrogen mixture, wherein the sintering temperature is 300-500 ℃, the heating rate of the temperature from room temperature to the sintering temperature is 1-5 ℃/min, and the sintering time is 8-15 hours; and after sintering, cooling to room temperature along with the furnace to obtain the surface-vulcanized lithium nickel manganese oxide cathode material.
The invention effectively changes the surface components of the lithium nickel manganese oxide positive electrode material by utilizing the vulcanization process, and improves the cycle performance and rate capability of the lithium nickel manganese oxide positive electrode material. The method has the advantages of simple process, low equipment requirement, low cost and easy industrial application.
Drawings
FIG. 1 is L iNi prepared in example 1 of the present invention0.5Mn1.5O4And surface-vulcanized L iNi0.5Mn1.5O4X-ray diffraction pattern of the sample.
FIG. 2 is a scanning electron micrograph of a sample prepared in example 1 of the present invention (a) L iNi0.5Mn1.5O4Surface-vulcanized L iNi0.5Mn1.5O4。
FIG. 3 is a graph of (a) cycle performance of samples prepared in example 1 of the present invention; (b) rate capability.
FIG. 4 is a scanning electron micrograph of a sample prepared in example 2 of the present invention (a) L iNi0.5Mn1.5O4Surface-vulcanized L iNi0.5Mn1.5O4。
FIG. 5 is a graph of the cycling performance of samples prepared in example 2 of the present invention (a) L iNi0.5Mn1.5O4Surface-vulcanized L iNi0.5Mn1.5O4。
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples.
Example 1
2.724 g of nickel acetate, 7.348 g of manganese acetate and 2.300 g of lithium acetate are weighed and dissolved in 400ml of deionized water, 13.142 g of tartaric acid is added after stirring continuously for 30 minutes at room temperature, ammonia water is dropped in the solution under stirring, the pH value of the solution is adjusted to be about 6.8, and then stirring continuously in a water bath at 90 ℃ until a gel liquid is obtained.
The gel liquid was dried in an air-blast drying oven at a temperature of 280 ℃ for 10 hours, and then the fluffy substance obtained after drying was ground to obtain a gel precursor powder.
Putting the collected gel precursor powder into a muffle furnace, calcining in air atmosphere, namely heating from room temperature to 500 ℃ at the heating rate of 3 ℃/s, sintering at 500 ℃ for 5 hours, then heating to 900 ℃ at the heating rate of 3 ℃/min, calcining at 900 ℃ for 12 hours, naturally cooling to room temperature along with the furnace after calcining, taking out the powder, grinding and sieving to obtain L iNi0.5Mn1.5O4And (3) a positive electrode material.
Weigh 0.027 grams L iNi0.5Mn1.5O4Dispersing the powder in 200ml of absolute ethyl alcohol, adding 1ml of 3-aminopropyltriethoxysilane after ultrasonic oscillation for 3 hours, fully reacting for 12 hours, washing with absolute ethyl alcohol and centrifugally separating for 10 times repeatedly, and vacuum drying to obtain L iNi with activated surface0.5Mn1.5O4And (3) powder.
L iNi activating the obtained surface0.5Mn1.5O4Dispersing the powder and 0.070 g thioacetamide in 100ml absolute ethyl alcohol, then dripping ammonia water under the stirring state, adjusting the pH value of the solution, controlling the pH value of the solution at 8.5, fully reacting for 4 hours, washing with absolute ethyl alcohol, centrifuging, and drying to obtain L iNi with sulfur ions adsorbed on the surface0.5Mn1.5O4And (3) powder.
L iNi having sulfur ion adsorbed on surface0.5Mn1.5O4Placing the powder in an atmosphere furnace, sintering in argon atmosphere at 400 deg.C with a heating rate of 3 deg.C/min from room temperature to sintering temperature for 12 hr, and cooling to room temperature to obtain surface-vulcanized L iNi0.5Mn1.5O4And (3) a positive electrode material.
FIG. 1 is a drawing ofAs shown in FIG. 1, the X-ray diffraction pattern of the sample prepared in this example shows that the diffraction peak of the synthesized powder is sharp, and the ratio of the intensity of the (111) diffraction peak to the intensity of the (311) diffraction peak is greater than 1.5, indicating L iNi0.5Mn1.5O4The XRD pattern of the surface in situ modified composite material was except L iNi0.5Mn1.5O4In addition to the diffraction peak of (1), a diffraction peak was observed at 27.62 ℃ and compared with MnS2The strongest main peak.
L iNi prepared by the present embodiment0.5Mn1.5O4The powder sample was subjected to electron scanning, as shown in FIG. 2 (a). L iNi0.5Mn1.5O4Scanning electron micrograph of the powder shows L iNi obtained0.5Mn1.5O4The powder has a regular polyhedral structure with smooth surface.
L iNi after surface vulcanization prepared in this example0.5Mn1.5O4Powder samples were subjected to electron microscopy as shown in FIG. 2 (b) L iNi after surface vulcanization0.5Mn1.5O4Scanning electron micrograph of the powder shows that the powder is L iNi0.5Mn1.5O4The surface of the material is subjected to in-situ surface modification to form a surface covering layer.
0.08 g of prepared L iNi was weighed0.5Mn1.5O4Dispersing powder, 0.01 g of conductive carbon black and 0.01 g of PVDF (polyvinylidene fluoride) binder in N-methylpyrrolidone solution, uniformly mixing, coating on an aluminum foil, and drying in vacuum at 120 ℃ for 12 hours to obtain L iNi0.5Mn1.5O4The anode adopts L iPF6/EC/DEC/DMC of 1.0 mol/L as electrolyte, wherein L iPF6The conductive salt is EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is a composite solvent, the volume ratio of EC to DEC to DMC is 1: 1: 1, a metal lithium sheet is used as a negative electrode, a Cellgard 2300 polypropylene film is used as a diaphragm, the positive electrode and the metal lithium sheet are assembled into a button cell, the button cell is charged and discharged at a current density of 2C (1C: 148mA/g), the charging and discharging voltage range is 3.0-4.9V, L iNi which is subjected to surface vulcanization is assembled in the same step0.5Mn1.5O4The button cell.
FIG. 3 is a charge-discharge cycle diagram showing L iNi at 25 ℃ and 2C magnification0.5Mn1.5O4The specific discharge capacity of the material can reach 120mAh/g, which shows that L iNi prepared by the method0.5Mn1.5O4The material has good electrochemical performance L iNi0.5Mn1.5O4Capacity retention rate after 1800 cycles of 45.3%, L iNi after surface vulcanization0.5Mn1.5O4The capacity retention rate after 2500 times of circulation is 74.9 percent, which shows that the method can greatly improve L iNi0.5Mn1.5O4The cycle stability of (c).
Example 2
Weighing 2.918 g of nickel nitrate, 7.364 g of manganese acetate and 1.421 g of lithium nitrate, dissolving the nickel nitrate, the manganese acetate and the lithium nitrate in 400ml of deionized water, continuously stirring the mixture at room temperature for 30 minutes, adding 12.621 g of citric acid, dripping ethylenediamine into the mixture under stirring, adjusting the pH value of the solution, controlling the pH value of the solution to be about 6.8, continuously stirring the mixture in a water bath at 85 ℃ until a gel-like liquid is obtained, placing the gel-like liquid in a forced air drying box at 260 ℃ for drying for 16 hours, grinding fluffy substances obtained after drying to obtain gel precursor powder, placing the collected gel precursor powder in a muffle furnace, calcining the gel precursor powder in an air atmosphere, heating the gel precursor powder from room temperature to 550 ℃ at a heating rate of 3 ℃/s, sintering the gel-like substance at 550 ℃ for 5 hours, then heating the gel-like substance at a heating rate of 3 ℃/min to 900 ℃, calcining the gel precursor powder at 900 ℃ for 15 hours, naturally cooling the furnace to room temperature after calcining, taking out the powder0.5Mn1.5O4And (3) a positive electrode material.
Weigh 0.024 grams L iNi0.5Mn1.5O4Dispersing the powder in 200ml of absolute ethyl alcohol, adding 2ml of 3-aminopropyltriethoxysilane after ultrasonic oscillation for 2 hours, fully reacting for 8 hours, washing with absolute ethyl alcohol and centrifugally separating for 10 times repeatedly, and vacuum drying to obtain L iNi with activated surface0.5Mn1.5O4L iNi obtained by surface activation0.5Mn1.5O4Dispersing the powder and 0.141 g thioacetamide in 100ml absolute ethyl alcohol, then dripping ammonia water under the stirring state, adjusting the pH value of the solution, controlling the pH value of the solution at 8.0, fully reacting for 3 hours, washing with absolute ethyl alcohol, centrifuging, and drying to obtain L iNi with sulfur ions adsorbed on the surface0.5Mn1.5O4L iNi having sulfur ion adsorbed on surface0.5Mn1.5O4Placing the powder in an atmosphere furnace, sintering in argon-hydrogen mixed gas atmosphere at the sintering temperature of 450 ℃, heating up from room temperature to the sintering temperature at the heating rate of 3 ℃/min for 10 hours, and cooling down to room temperature along with the furnace after sintering to obtain L iNi with vulcanized surface0.5Mn1.5O4And (3) a positive electrode material.
In FIG. 4, (a) is L iNi0.5Mn1.5O4Scanning electron micrograph of the powder showed L iNi obtained0.5Mn1.5O4The powder has a regular polyhedral structure with smooth surface (b) in FIG. 4 is surface-vulcanized L iNi0.5Mn1.5O4Scanning Electron micrograph of powder, compare L iNi0.5Mn1.5O4The particles are present on the surface of the surface-vulcanized sample.
0.08 g of prepared L iNi was weighed0.5Mn1.5O4Dispersing powder, 0.01 g of conductive carbon black and 0.01 g of PVDF (polyvinylidene fluoride) binder in N-methylpyrrolidone solution, uniformly mixing, coating on an aluminum foil, and drying in vacuum at 120 ℃ for 12 hours to obtain L iNi0.5Mn1.5O4The anode adopts L iPF6/EC/DEC/DMC of 1.0 mol/L as electrolyte, wherein L iPF6The conductive salt is EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is a composite solvent, the volume ratio of EC to DEC to DMC is 1: 1: 1, a metal lithium sheet is used as a negative electrode, a Cellgard 2300 polypropylene film is used as a diaphragm, the positive electrode and the metal lithium sheet are assembled into a button cell, the button cell is charged and discharged at a current density of 2C (1C: 148mA/g), the charging and discharging voltage range is 3.0-4.9V, L iNi which is subjected to surface vulcanization is assembled in the same step0.5Mn1.5O4The button cell.
FIG. 5 is a charge-discharge cycle diagram showing L iNi at 25 ℃ and 2C magnification0.5Mn1.5O4The specific discharge capacity of the material can reach 125mAh/g, which shows that L iNi prepared by the method0.5Mn1.5O4The material has good electrochemical performance L iNi0.5Mn1.5O4Capacity retention rate after 500 cycles of 69.1%, L iNi after surface vulcanization0.5Mn1.5O4The capacity retention rate is 80% after 500 times of circulation, which shows that the method can greatly improve L iNi0.5Mn1.5O4The cycle stability of (c).
Claims (7)
1. A method for vulcanizing the surface of a spinel lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps:
1) respectively mixing soluble L i, Ni and Mn compounds according to the proportion of (1) - (1)x) Dissolving the mixture in deionized water in a molar ratio of 0.5:1.5, and fully stirring to obtain a clear mixed solution, wherein the molar ratio is more than or equal to 0x≤0.1;
2) Adding a metal ion chelating agent into the mixed solution, stirring for 6-10 hours, and then adjusting the pH value of the solution by using ammonia water or ethylenediamine, wherein the pH value range is 6-7;
3) placing the mixed solution in a water bath kettle at the temperature of 80-90 ℃ to continue stirring and refluxing, and stirring for 8-24 hours to obtain gel liquid;
4) placing the gel liquid in a blast drying oven or a muffle furnace, carrying out heat treatment for 8-24 hours at 250-280 ℃ in the air atmosphere to obtain a fluffy substance, and grinding to obtain gel precursor powder;
5) placing the collected gel precursor powder in an atmosphere furnace, calcining in two stages in the air or oxygen atmosphere, and cooling to room temperature along with the furnace after calcination is finished to obtain the lithium nickel manganese oxide cathode material:
6) dispersing the prepared lithium nickel manganese oxide positive electrode material powder in absolute ethyl alcohol, adding 3-aminopropyl triethoxysilane after ultrasonic oscillation for 2-6 hours, fully reacting for 5-15 hours, washing with absolute ethyl alcohol, centrifugally separating, and drying to obtain surface-activated lithium nickel manganese oxide powder;
7) weighing a certain mass of surface-activated lithium nickel manganese oxide powder and thioacetamide, dispersing the powder and the thioacetamide in absolute ethyl alcohol, then adjusting the pH value of the solution by using ammonia water or ethylenediamine, wherein the pH value range is 7.5-8.5, washing the solution by using absolute ethyl alcohol after reacting for 3-6 hours, carrying out centrifugal separation, and then drying the solution to obtain the lithium nickel manganese oxide powder with sulfur ions adsorbed on the surface;
8) placing the lithium nickel manganese oxide powder with sulfur ions adsorbed on the surface in an atmosphere furnace, sintering in the atmosphere of argon or argon-hydrogen mixture, wherein the sintering temperature is 300-500 ℃, the heating rate of the temperature from room temperature to the sintering temperature is 1-5 ℃/min, and the sintering time is 8-15 hours; and after sintering, cooling to room temperature along with the furnace to obtain the surface-vulcanized lithium nickel manganese oxide cathode material.
2. The method for sulfurizing the surface of a spinel lithium nickel manganese oxide cathode material according to claim 1, wherein said soluble L i compound is one of lithium acetate, lithium nitrate and lithium sulfate.
3. The method for sulfurizing the surface of a spinel lithium nickel manganese oxide cathode material according to claim 1, wherein the soluble Ni compound is one of nickel acetate, nickel nitrate and nickel sulfate.
4. The method for sulfurizing the surface of a spinel lithium nickel manganese oxide cathode material according to claim 1, wherein the soluble Mn compound is one of manganese acetate, manganese nitrate and manganese sulfate.
5. The method of claim 1, wherein the metal ion chelating agent is one of oxalic acid, citric acid and tartaric acid, and the amount of the metal ion chelating agent is 2.0-4.0 times of the total molar amount of all metal ion substances in the mixed solution.
6. The method for sulfurizing the surface of a spinel lithium nickel manganese oxide positive electrode material according to claim 1, wherein the amount of 3-aminopropyl triethoxysilane is 0.5-3 ml 3-aminopropyl triethoxysilane for 0.03 g lithium nickel manganese oxide.
7. The method for sulfidizing the surface of the spinel lithium nickel manganese oxide cathode material according to the claim 1, wherein the two-stage calcination is carried out, the first stage: the calcination temperature is 450-550 ℃, the temperature rising rate from the room temperature to the calcination temperature is 1-5 ℃/min, and the calcination time is 3-8 hours; and a second stage: the calcination temperature is 850-950 ℃, the temperature rising rate from the first stage calcination temperature to the second stage calcination temperature is 2-5 ℃/min, and the calcination time is 9-20 hours.
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| US7771497B1 (en) * | 2005-01-19 | 2010-08-10 | Greatbatch Ltd. | Method of using cyclic pressure to increase the planarity of SVO/current collector/CFX electrodes for use in lithium electrochemical cells |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
| CN105789568A (en) * | 2014-12-16 | 2016-07-20 | 绍兴文理学院 | Sulfur element doped lithium-rich lithium manganese oxide material and preparation method thereof |
| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7771497B1 (en) * | 2005-01-19 | 2010-08-10 | Greatbatch Ltd. | Method of using cyclic pressure to increase the planarity of SVO/current collector/CFX electrodes for use in lithium electrochemical cells |
| CN105789568A (en) * | 2014-12-16 | 2016-07-20 | 绍兴文理学院 | Sulfur element doped lithium-rich lithium manganese oxide material and preparation method thereof |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
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