CN103078098A - Preparation method of lithium-rich layered manganese-cobalt oxide composite positive electrode material - Google Patents
Preparation method of lithium-rich layered manganese-cobalt oxide composite positive electrode material Download PDFInfo
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- CN103078098A CN103078098A CN201110329084XA CN201110329084A CN103078098A CN 103078098 A CN103078098 A CN 103078098A CN 201110329084X A CN201110329084X A CN 201110329084XA CN 201110329084 A CN201110329084 A CN 201110329084A CN 103078098 A CN103078098 A CN 103078098A
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Abstract
The invention relates to a preparation method of a lithium-rich layered manganese-cobalt solid solution composite positive electrode material. According to the invention, metal salt and a hydroxide are subjected to a solid-state reaction under room temperature, such that a nano-grade precursor is obtained; in a subsequent heat treatment process, metal salt in the precursor is adopted as a flux, and reactants in the precursor sufficiently contact, mix, and diffuse in the flux, such that a rapid reaction purpose is achieved. Therefore, a solid solution composite positive electrode material xLi2MnO3.(1-x)LiCoO2 (x=0.1-1.0) micro-nano particle structure is prepared. A lithium ion battery assembled by using the solid solution composite positive electrode material synthesized with the method provided by the invention has stable electrochemical performance and cycle performance, and good reproducibility.
Description
Technical field
The present invention relates to the preparation method of a kind of rich lithium Layered Manganese cobalt/cobalt oxide composite positive pole in the lithium ion battery field.
Background technology
The advantage such as lithium ion battery has high voltage, high power capacity, has extended cycle life, security performance is good makes it have broad application prospects in fields such as portable electric appts, electric automobile, space technologies.Exploitation high-energy-density and high power density lithium ion battery are present study hotspots.Because anode material for lithium-ion batteries commonly used is such as LiFePO
4, LiCoO
2, LiMn
2O
4Deng capacity lower (＜200mAh/g), high temperature performance is poor, can not satisfy the requirement of electrokinetic cell capacity development.Composite positive pole xLi
2MnO
3(1-x) LiCoO
2Cause showing great attention to of people, be considered to have one of candidate's positive electrode of the high power capacity power lithium-ion battery of excellent cryogenic property.The method of this type of composite positive pole of preparation of bibliographical information has sol-gal process, ion-exchange, solid sintering technology etc. at present.Sol-gal process and ion-exchange technique are loaded down with trivial details, are not suitable for large-scale industrial production.Although solid sintering technology technique is simple, is easy to expanding production, its batch mixing uniformity is relatively poor, synthetic material repeated relatively poor.The present invention adopts a kind of simple molten salt growth method to prepare solid solution class composite positive pole xLi
2MnO
3(1-x) LiCoO
2(x=0.1～1.0), this preparation method is simple, practical, efficient, low cost, and prepared material has excellent chemical property.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of rich lithium Layered Manganese cobalt/cobalt oxide composite positive pole.
The preparation method of a kind of rich lithium Layered Manganese cobalt/cobalt oxide composite positive pole provided by the invention is characterized in that: adopting the general formula of the rich lithium Layered Manganese cobalt/cobalt oxide composite positive pole of the method preparation is xLi
2MnO
3(1-x) LiCoO
2, x=0.1～1.0, its primary particle has the micro-nano granules structure, and average grain diameter is 600～1000nm, and specific area is 0.20～0.80m
2/ g; This preparation method may further comprise the steps:
(1) at first according to composite material xLi
2MnO
3(1-x) LiCoO
2, the composition of x=0.1～1.0 takes by weighing lithium salts, manganese and cobalt salt according to Mol ratio, and batch mixing is ground or ball milling;
(2) in the batch mixing that in step (1), obtains in hydroxyl: total metal ion=(2.0～5.0): 1 ratio adds hydroxide;
(3) step (2) gained mixture is ground or ball milling, the dry processing obtains the black cake mass after the processing;
The cake mass of the black that (4) step (3) is obtained carries out sintering reaction after grinding fully.Heat treated was divided into for two steps, added at low temperatures thermal response a period of time first, then be warmed up to high temperature and carry out the second step reaction, and afterproduct cools to the cake mass that room temperature obtains grey black with the furnace, this material is repeatedly washed with deionized water obtain residue;
(5) residue that step (4) is obtained carries out drying to be processed, and obtains Primary product;
(6) heat treated a period of time at low temperatures behind the Primary product compressing tablet that step (5) is obtained, then be warmed up to higher heat-treated a period of time, material cooling after will processing at last, can obtain final solid solution class composite material, this material can be used as the positive electrode of lithium ion battery.
Lithium salts described in the above-mentioned steps (1) is one or more in lithium acetate, lithium nitrate, the lithium chloride; Described manganese salt is one or more in manganese acetate, manganese nitrate, the manganese chloride; Described cobalt salt is one or more in cobalt acetate, cobalt nitrate, the cobalt chloride.
Hydroxide described in the above-mentioned steps (2) is one or more in NaOH, potassium hydroxide, magnesium hydroxide, the calcium hydroxide.
The time of grinding or ball-milling treatment is 2～10h in the above-mentioned steps (3); The dry temperature of processing is 160 ℃～200 ℃, and the processing time is 2～12h.
In two steps of heating process, the Low Temperature Thermal temperature is 300～350 ℃ in the above-mentioned steps (4), and the time is 8～12h, and high warm temperatures is 800 ℃～1000 ℃, and the time is 8～20h.
The dry temperature of processing is 160 ℃～200 ℃ in the above-mentioned steps (5), and the processing time is 2～12h.
The low-temp reaction temperature is 450～550 ℃ in the above-mentioned steps (6), and the time is 3～6h; The pyroreaction temperature is 800 ℃～1000 ℃, and the time is 8～20h; The mode that cooling is used has annealing at room temperature, and the sample that obtains after the annealing in process is the rich lithium Layered Manganese of end product cobalt/cobalt oxide composite positive pole, and it can be used as anode material for lithium-ion batteries.
The present invention utilizes the synthetic process characteristic of molten salt growth method, utilizes product salt that slaine and hydroxide generates at room temperature reaction as the required flux of molten salt growth method, helps to accelerate the ion diffusion in the molten salt react ion, has greatly improved the uniformity coefficient of reaction speed and reaction.The raw material sources that the present invention adopts are extensive, and process engineering is simple, and preparation parameter is easy to control, and good reproducibility can synthesize in scale, and device therefor is simple, and the salt that utilizes the course of reaction generation has been saved production cost as flux.Adopt the rich lithium solid solution of the stratiform class composite positive pole of the inventive method preparation as the electrode material of lithium ion battery, can improve chemical property and the cycle performance of lithium ion battery product.This richness lithium Layered Manganese cobalt/cobalt oxide composite positive pole stable performance, favorable reproducibility is that 750nm, specific area are 0.42m for particle mean size
2/ g consists of 0.6Li
2MnO
30.4LiCoO
2Composite material, in the charging/discharging voltage scope of 2.0～4.8V, when it discharged and recharged 30,50, under the current density of 80mA/g and 100mA/g, the first discharge specific capacity of composite material was respectively 226.0,184.5,149.9mAh/g and 139.2mAh/g.
Description of drawings
Fig. 1 consists of xLi among the serial embodiment
2MnO
3(1-x) LiCoO
2The X-ray diffracting spectrum of (x=0.1～1.0) composite material.
Fig. 2 is 0.6Li among the embodiment 1
2MnO
30.4LiCoO
2The stereoscan photograph of composites pattern.
Fig. 3 is 0.6Li among the embodiment 1
2MnO
30.4LiCoO
2The stereoscan photograph of class solid solution composite material part.
Fig. 4 is that embodiment 1 is by 0.6Li
2MnO
30.4LiCoO
2Composite material is as the first constant current charge-discharge curve of positive pole when different charging and discharging currents density (30,50,80mA/g and 100mA/g).
Fig. 5 is that embodiment 1 is by 0.6Li
2MnO
30.4LiCoO
2Composite material is as the specific discharge capacity attenuation curve of positive pole under above-mentioned current density.
Embodiment
Main implementation process of the present invention is:
(1) at first according to composite material xLi
2MnO
3(1-x) LiCoO
2, the composition of x=0.1～1.0 takes by weighing lithium salts, manganese and cobalt salt according to Mol ratio, and batch mixing is ground or ball milling;
(2) in the batch mixing that in step (1), obtains in hydroxyl: total metal ion=(2.0～5.0): 1 ratio adds hydroxide;
(3) step (2) gained mixture is ground or ball-milling treatment 2～10h, then at 160 ℃～200 ℃ dry 2～12h that process, obtain the black cake mass after the processing;
After the cake mass of the black that (4) step (3) is obtained grinds fully, heat-treat, heat treated was divided into for two steps, first add thermal response 8～12h at 300～350 ℃, then be warmed up to 800 ℃～1000 ℃, insulation 8～20h cools to the cake mass that room temperature obtains grey black with the furnace, this material is repeatedly washed with deionized water obtain residue;
(5) residue that step (4) is obtained carries out drying at 160 ℃～200 ℃ and processes 2～12h, obtains Primary product;
(6) be heated to 450～550 ℃ of insulation 3～6h behind the Primary product compressing tablet that step (5) is obtained, then be warmed up to 800 ℃～1000 ℃ reaction 8～20h.Be annealed at last room temperature, namely obtain final rich lithium Layered Manganese cobalt/cobalt oxide composite material.This material can be used as the positive electrode of lithium ion battery.
Below further illustrate characteristics of the present invention by example, but be not limited to embodiment.
Experimental technique among the following embodiment if no special instructions, is conventional method.
Embodiment 1:0.6Li
2MnO
30.4LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 1.4722g manganese acetate, 0.9985g cobalt acetate, 1.7148g lithium acetate and 3.1236g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace.This material is repeatedly washed with deionized water, obtain residue.The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product.At 900 ℃ of heat treatment 12h, the product after will processing at last is annealed to room temperature, can obtain final target product 0.6Li with Primary product
2MnO
30.4LiCoO
2This product can be used as the positive electrode of lithium ion battery.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.6Li that forms
2MnO
30.4LiCoO
2Approach.The X-ray diffraction test result of synthetic composite material shows, the corresponding stratiform rock salt structure (R-3m) in the spectrum peak of sample, and laminar composite has been synthesized in 20～25 ° special spectrum peak structure explanation.The stereoscan photograph of powder shows that material granule disperses better and be big or small than homogeneous, and the Average Particle Diameters of particle is about 750nm.The BET test shows that the specific surface area size of synthetic material is 0.42m
2/ g.Fig. 4 and Fig. 5 are respectively composite positive pole 0.6Li
2MnO
30.4LiCoO
2First charge-discharge curve under different current densities and specific discharge capacity attenuation curve.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and binding agent PVDF (Kynoar) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is electrolyte, and polypropylene material is barrier film, and battery test system is LAND CT2001A, and the charging/discharging voltage scope is 2.0～4.8V, and charging and discharging currents density is chosen respectively 30mAg
-1, 50mAg
-1, 80mAg
-1, 100mAg
-1This material shows good chemical property during as lithium ion battery anodal, at 30mAg
-1, 50mAg
-1, 80mAg
-1, 100mAg
-1Charging and discharging currents density under first discharge specific capacity be respectively 226.0mAhg
-1, 184.5mAhg
-1, 149.9mAhg
-1, 139.2mAhg
-1, cycle performance is basicly stable, and after discharging and recharging through 15 times, their specific discharge capacity is respectively 153.5mAhg
-1, 166.0mAhg
-1, 145.9mAhg
-1, 130.9mAhg
-1
Embodiment 2:0.1Li
2MnO
30.9LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 0.2470g manganese acetate, 2.2478g cobalt acetate, 1.1795g lithium acetate and 2.5223g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace; This material is repeatedly washed with deionized water, obtain residue; The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product; At 900 ℃ of heat treatment 12h, the product after will processing at last is annealed to room temperature, can obtain target product with Primary product.This product can be used as the positive electrode of lithium ion battery.The X-ray diffraction test result shows that synthetic material has stratiform rock salt structure (R-3m), is rich lithium laminar composite.The sem test result shows that the Average Particle Diameters of synthetic material is about 600nm.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.1Li that forms
2MnO
30.9LiCoO
2Approach.The BET test shows that the specific surface area size of synthetic material is 0.20m
2/ g.The button cell test shows that when charging and discharging currents density size was 30mA/g, the first charge-discharge specific capacity of material was respectively 246.3mAh/g and 173.0mAh/g; When charging and discharging currents density size was 50mA/g, the first charge-discharge specific capacity size of material was respectively 269.1mAh/g and 203.3mAh/g; When charging and discharging currents density size was 80mAh/g, the first charge-discharge specific capacity size of material was respectively 271.7mAh/g and 205.9mAh/g; When charging and discharging currents density size was 100mAh/g, the first charge-discharge specific capacity size of material was respectively 257.9mAh/g and 206.8mAh/g.
Embodiment 3:0.2Li
2MnO
30.8LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 0.4919g manganese acetate, 1.9971g cobalt acetate, 1.2866g lithium acetate and 2.6419g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace; This material is repeatedly washed with deionized water, obtain residue; The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product; At 900 ℃ of heat treatment 16h, the product after will processing at last is annealed to room temperature, can obtain final target product with Primary product, and this product can be used as the positive electrode of lithium ion battery.The X-ray diffraction test result shows that synthetic material has stratiform rock salt structure (R3m), is rich lithium laminar composite.The sem test result shows that the Average Particle Diameters of synthetic material is about 800nm.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.2Li that forms
2MnO
30.8LiCoO
2Approach.The BET test shows that the specific surface area size of synthetic material is 0.50m
2/ g.The button cell test shows that when charging and discharging currents density size was 30mA/g, the first charge-discharge specific capacity of material was respectively 257.3mAh/g and 176.7mAh/g; When charging and discharging currents density size was 50mA/g, the first charge-discharge specific capacity size of material was respectively 259.5mAh/g and 179.6mAh/g; When charging and discharging currents density size was 80mAh/g, the first charge-discharge specific capacity size of material was respectively 259.7mAh/g and 175.3mAh/g; When charging and discharging currents density size was 100mAh/g, the first charge-discharge specific capacity size of material was respectively 249.0mAh/g and 175.3mAh/g.
Embodiment 4:0.3Li
2MnO
30.7LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 0.7374g manganese acetate, 1.7458g cobalt acetate, 1.3974g lithium acetate and 2.7628g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace; This material is repeatedly washed with deionized water, obtain residue; The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product; At 900 ℃ of heat treatment 12h, the product after will processing at last is annealed to room temperature, can obtain final target product with Primary product, and this product can be used as the positive electrode of lithium ion battery.The X-ray diffraction test result shows that synthetic material has stratiform rock salt structure (R3m), is rich lithium laminar composite.The sem test result shows that the Average Particle Diameters of synthetic material is about 900nm.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.3Li that forms
2MnO
30.7LiCoO
2Approach.The BET test shows that the specific surface area size of synthetic material is 0.62m
2/ g.The button cell test shows that when charging and discharging currents density size was 30mA/g, the first charge-discharge specific capacity of material was respectively 345.4mAh/g and 144.8mAh/g; When charging and discharging currents density size was 50mA/g, the first charge-discharge specific capacity size of material was respectively 274.6mAh/g and 168.4mAh/g; When charging and discharging currents density size was 80mAh/g, the first charge-discharge specific capacity size of material was respectively 303.7mAh/g and 164.8mAh/g; When charging and discharging currents density size was 100mAh/g, the first charge-discharge specific capacity size of material was respectively 276.1mAh/g and 162.5mAh/g.
Embodiment 5:0.4Li
2MnO
30.6LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 0.9846g manganese acetate, 1.4955g cobalt acetate, 1.5018g lithium acetate and 2.8818g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace; This material is repeatedly washed with deionized water, obtain residue; The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product; At 900 ℃ of heat treatment 12h, the product after will processing at last is annealed to room temperature, can obtain final target product with Primary product, and this product can be used as the positive electrode of lithium ion battery.The X-ray diffraction test result shows that synthetic material has stratiform rock salt structure (R3m), is rich lithium laminar composite.The sem test result shows that the Average Particle Diameters of synthetic material is about 1000nm.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.4Li that forms
2MnO
30.6LiCoO
2Approach.The BET test shows that the specific surface area size of synthetic material is 0.80m
2/ g.The button cell test shows that when charging and discharging currents density size was 30mA/g, the first charge-discharge specific capacity of material was respectively 330.2mAh/g and 216.2mAh/g; When charging and discharging currents density size was 50mA/g, the first charge-discharge specific capacity size of material was respectively 287.5mAh/g and 176.2mAh/g; When charging and discharging currents density size was 80mAh/g, the first charge-discharge specific capacity size of material was respectively 302.8mAh/g and 190.2mAh/g; When charging and discharging currents density size was 100mAh/g, the first charge-discharge specific capacity size of material was respectively 259.6mAh/g and 152.2mAh/g.
Embodiment 6:0.7Li
2MnO
30.3LiCoO
2The preparation of positive electrode
With lithium acetate, manganese acetate, cobalt acetate, NaOH is initiation material, takes by weighing 1.7167g manganese acetate, 0.7485g cobalt acetate, 1.8245g lithium acetate and 3.2440g NaOH.With batch mixing ball milling 2h at room temperature, 180 ℃ of lower dry 4h of the batch mixing behind the ball milling are obtained the cake masss of black; After the cake mass grinding fully with black, first at 350 ℃ of heat treated 10h, then be warmed up to 900 ℃ of heat treatment 12h, cool to the cake mass that room temperature obtains grey black with the furnace; This material is repeatedly washed with deionized water, obtain residue; The residue that obtains is carried out drying at 180 ℃ process 6h, obtain Primary product; At 900 ℃ of heat treatment 12h, the product after will processing at last is annealed to room temperature, can obtain final target product with Primary product, and this product can be used as the positive electrode of lithium ion battery.The X-ray diffraction test result shows that synthetic material has stratiform rock salt structure (R3m), is rich lithium laminar composite.The sem test result shows that the Average Particle Diameters of synthetic material is about 850nm.The actual composition of the plasma emission spectrogram display material of synthetic material and the theoretical 0.7Li that forms
2MnO
30.3LiCoO
2Approach.The BET test shows that the specific surface area size of synthetic material is 0.75m
2/ g.The button cell test shows that when charging and discharging currents density size was 30mA/g, the first charge-discharge specific capacity of material was respectively 297.6mAh/g and 195.3mAh/g; When charging and discharging currents density size was 50mA/g, the first charge-discharge specific capacity size of material was respectively 274.6mAh/g and 172.3mAh/g; When charging and discharging currents density size was 80mAh/g, the first charge-discharge specific capacity size of material was respectively 258.4mAh/g and 148.5mAh/g; When charging and discharging currents density size was 100mAh/g, the first charge-discharge specific capacity size of material was respectively 249.7mAh/g and 132.5mAh/g.
Claims (5)
1. the preparation method of a rich lithium Layered Manganese cobalt/cobalt oxide composite positive pole, it is characterized in that: this preparation method may further comprise the steps:
(1) at first according to composite material xLi
2MnO
3(1-x) LiCoO
2, the composition of x=0.1～1.0 takes by weighing lithium salts, manganese and cobalt salt according to Mol ratio, and batch mixing is ground;
(2) in the batch mixing that in step (1), obtains in hydroxyl: total metal ion=(2.0～5.0): 1 ratio adds hydroxide;
(3) step (2) gained mixture is ground, the dry processing obtains the black cake mass after the processing;
After the cake mass of the black that (4) step (3) is obtained grinds fully, first at 300～350 ℃ of heating 8～12h, then be warming up to 800 ℃～1000 ℃ heating 8～20h, cool at last the cake mass that room temperature obtains grey black with the furnace, this material is repeatedly washed with deionized water obtain residue;
(5) residue that step (4) is obtained carries out drying to be processed, and obtains Primary product;
(6) heat 3～6h at 450～550 ℃ behind the Primary product compressing tablet that step (5) is obtained, then be warming up to 800 ℃～1000 ℃, heating 8～20h, the product after will processing at last is cooled to room temperature, namely obtains final rich lithium Layered Manganese cobalt composite material.
2. the preparation method of positive electrode according to claim 1, it is characterized in that: the lithium salts described in the described step (1) is selected from one or more in lithium acetate, lithium nitrate, the lithium chloride; Described manganese salt is selected from one or more in manganese acetate, manganese nitrate, the manganese chloride; Described cobalt salt is selected from one or more in cobalt acetate, cobalt nitrate, the cobalt chloride.
3. described method according to claim 1, it is characterized in that: used hydroxide is selected from one or several in NaOH, potassium hydroxide, magnesium hydroxide, the calcium hydroxide in the described step (2).
4. described method according to claim 1, it is characterized in that: the dry temperature of processing is 160 ℃～200 ℃ in the described step (3), and the processing time is 2～12h.
5. described method according to claim 1, it is characterized in that: the dry temperature of processing is 160 ℃～200 ℃ in the described step (5), and the processing time is 2～12h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751481A (en) * | 2012-02-14 | 2012-10-24 | 中国科学院福建物质结构研究所 | Li2MnO3 and LiCoO2 composite anode material |
| CN104016421A (en) * | 2014-06-24 | 2014-09-03 | 南通瑞翔新材料有限公司 | Preparation method for lithium ion positive electrode material |
| CN105914363A (en) * | 2016-04-29 | 2016-08-31 | 复旦大学 | Lithium-rich layered cathode material of lithium ion battery, and preparation method and application of lithium-rich layered cathode material |
| CN109742449A (en) * | 2018-12-15 | 2019-05-10 | 桂林理工大学 | A kind of preparation method of NASICON type solid electrolyte |
| KR20200093020A (en) * | 2017-12-18 | 2020-08-04 | 다이슨 테크놀러지 리미티드 | Use of cobalt in a lithium-rich cathode material to increase the filling capacity of the cathode material and suppress gas evolution from the cathode material during the charging cycle |
| CN114314671A (en) * | 2022-01-07 | 2022-04-12 | 哈尔滨工业大学 | High-capacity lithium-manganese-oxygen-rich cathode material and preparation method thereof |
| WO2024011621A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Lithium manganese iron phosphate positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electric device |
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| CN101677125A (en) * | 2008-09-16 | 2010-03-24 | 中国科学院福建物质结构研究所 | Method for preparing layered cathode material of lithium ion battery |
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| CN102751481A (en) * | 2012-02-14 | 2012-10-24 | 中国科学院福建物质结构研究所 | Li2MnO3 and LiCoO2 composite anode material |
| CN104016421A (en) * | 2014-06-24 | 2014-09-03 | 南通瑞翔新材料有限公司 | Preparation method for lithium ion positive electrode material |
| CN104016421B (en) * | 2014-06-24 | 2016-05-04 | 南通瑞翔新材料有限公司 | A kind of preparation method of lithium ion anode material |
| CN105914363A (en) * | 2016-04-29 | 2016-08-31 | 复旦大学 | Lithium-rich layered cathode material of lithium ion battery, and preparation method and application of lithium-rich layered cathode material |
| KR20200093020A (en) * | 2017-12-18 | 2020-08-04 | 다이슨 테크놀러지 리미티드 | Use of cobalt in a lithium-rich cathode material to increase the filling capacity of the cathode material and suppress gas evolution from the cathode material during the charging cycle |
| KR102586687B1 (en) | 2017-12-18 | 2023-10-11 | 다이슨 테크놀러지 리미티드 | Use of cobalt in lithium-rich cathode materials to increase the charging capacity of the cathode material and to suppress outgassing from the cathode material during the charging cycle. |
| CN109742449A (en) * | 2018-12-15 | 2019-05-10 | 桂林理工大学 | A kind of preparation method of NASICON type solid electrolyte |
| CN109742449B (en) * | 2018-12-15 | 2022-02-15 | 桂林理工大学 | Preparation method of NASICON type solid electrolyte |
| CN114314671A (en) * | 2022-01-07 | 2022-04-12 | 哈尔滨工业大学 | High-capacity lithium-manganese-oxygen-rich cathode material and preparation method thereof |
| WO2024011621A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Lithium manganese iron phosphate positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electric device |
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