CN106856238A - A kind of positive electrode and preparation method thereof - Google Patents
A kind of positive electrode and preparation method thereof Download PDFInfo
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- CN106856238A CN106856238A CN201611233185.6A CN201611233185A CN106856238A CN 106856238 A CN106856238 A CN 106856238A CN 201611233185 A CN201611233185 A CN 201611233185A CN 106856238 A CN106856238 A CN 106856238A
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- positive electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of positive electrode and preparation method, the positive electrode prepared with the method, its pattern is self assembly ball, and specific implementation step is：(1) manganese salt, chromic salts and graphene oxide are dissolved in the mixed liquid of water or water and ethanol；(2) lithium salts is dissolved in water, is poured into the solution that step (1) is obtained；(3) solution that step (2) is obtained is evaporated under proper temperature；(4) presoma for obtaining step (3) under air prior to after lower temperature heat treatment a period of time, then being transferred under inert gas shielding and carrying out high-temperature heat treatment and can obtain target positive electrode.Compared with prior art, the preparation method is characterised by spinelle and layered cathode material being carried out into In-situ reaction with Graphene, thus obtained by positive electrode have very excellent high rate performance, with specific capacity it is high, high rate performance is excellent and has extended cycle life the features such as.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of positive electrode and preparation method thereof.
Background technology
With electric motor car and the popularization of portable electric appts, with high power density, high-energy-density, long circulating longevity
The lithium ion battery of life, high-volume and capacity ratio and high security has become the final goal of current research.The lithium commonly used at present
Cell positive material is NCA and MCN, but contains cobalt element in both positive electrodes, causes being produced into for whole material
This is higher.Meanwhile, the performance of lithium ion battery each side depends greatly on the performance of positive electrode, so compeling now
Being essential will further improve volumetric properties, high rate performance and the cyclical stability of positive electrode.So far, common positive pole
In material, layered oxide positive electrode has highest theoretical specific capacity, is a kind of unique theoretical specific capacity close to 300mAh
g-1Positive electrode.However, the high rate performance of current layered oxide positive electrode is far from practical application is met, being badly in need of will
Further improve.In order to improve its high rate performance, many improved methods are nowadays had reported, such as：Carbon coating and and graphite
Alkene is combined.Regrettably, because the preparation of layered oxide positive electrode is typically to be carried out under the oxygen containing atmosphere of high temperature, therefore
The surface treatment means of above-mentioned ex situ are not significantly improved the high rate performance of layered oxide positive electrode.
The content of the invention
The purpose of the present invention is exactly to provide a kind of good rate capability, ratio for the defect for overcoming above-mentioned prior art to exist
Big positive electrode of capacity and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：A kind of positive electrode, the positive electrode includes
Spherical lithium manganese chromated oxide and the Graphene of the sheet being plugged between spherical lithium manganese chromated oxide, the lithium manganese chromium oxidation
The molecular formula of thing is xLi2MO3·yLiM2O4·(1-x-y)LiMO2, wherein, the ＜ 1-x-y ＜ 1 of 0 ＜ x ＜, 1,0 ＜ y ＜ 1,0, M generations
The mass ratio of table Mn and/or Cr, the lithium manganese chromated oxide and Graphene is 100：(0.5~5).
Preferably, described 0.3≤x≤0.6,0.01≤y≤0.2.
Compared with Current commercial layered cathode material (NCA or MCN), the chemistry of lithium in lithium manganese chromated oxide of the invention
Stoichiometric number is more than 1, is rich lithium type positive electrode, thus with specific capacity high.And, shown by X-ray diffraction, this hair
Bright positive electrode is stratiform and Spinel positive electrode and the In-situ reaction of Graphene.Spinel in composite has
Beneficial to the transmission of lithium ion, and Graphene can greatly improve the electronic conductivity of material, so the positive electrode has
Very excellent high rate performance.
A kind of preparation method of positive electrode as described above, including following steps：
(1) lithium salts, manganese salt, chromic salts and Graphene are weighed in proportion, manganese salt and chromic salts are dissolved, obtain mixed solution, will
In Graphene ultrasonic disperse to mixed solution, lithium salts dissolving is then added, obtain precursor solution；
(2) precursor solution is evaporated, is dried, then carry out Low Temperature Heat Treatment, obtain powder body material；
(3) powder body material is carried out into high-temperature heat treatment under high temperature, inert gas environment, cooling obtains final product the positive pole material
Material.
Described lithium salts is one or more in lithium acetate, lithium nitrate, lithium chloride, lithium carbonate；The manganese salt is acetic acid
One or more in manganese, manganese nitrate, manganese chloride；The chromic salts is one or more in chromium acetate, chromic nitrate, chromium chloride.
The manganese salt and chromic salts are dissolved in the mixed liquor of absolute ethyl alcohol or water or both.
The temperature that the precursor solution is evaporated be 50 DEG C~160 DEG C, drying temperature be 160 DEG C~250 DEG C, drying time
3~24h.
The Low Temperature Heat Treatment is carried out in Muffle furnace, and treatment temperature is 300~500 DEG C, and process time is 1~24h,
At this temperature, the manganese element that precursor solution is dried in gained material is oxidized to+4 valencys.
The high-temperature heat treatment is carried out in tube furnace, and treatment temperature is 600~800 DEG C, 6~24h of process time.At this
At a temperature of, each mutually shaping in powder body material obtains the In-situ reaction of stratiform and Spinel lithium manganese chromated oxide and Graphene
Material.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) stoichiometric number of lithium is more than 1 in lithium manganese chromated oxide, is rich lithium type positive electrode, with specific capacity high；
(2) Spinel and the in situ of Graphene introduce the high rate performance for substantially increasing the positive electrode；
(3) when preparing, sintering temperature is low, reduces production cost, has saved the energy；
(4) cobalt element is free of in positive electrode of the invention, the production cost of positive electrode is reduced.
Brief description of the drawings
Fig. 1 is the Li of embodiment 11.2Mn0.6Cr0.2OzThe X-ray diffracting spectrum of/graphene anode material.
Fig. 2 is the Li of embodiment 11.2Mn0.6Cr0.2OzThe SEM figures of/graphene anode material.
Fig. 3 is the Li of embodiment 11.2Mn0.6Cr0.2Oz/ graphene anode material 100mAg at room temperature-1Shi Shouci and second
Secondary charging and discharging curve.
Fig. 4 is the Li of embodiment 11.2Mn0.6Cr0.2Oz/ graphene anode material 600mAg at room temperature-1When cycle performance
Curve.
Fig. 5 is the Li of embodiment 11.2Mn0.6Cr0.2Oz/ graphene anode material high rate performance figure at room temperature.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
Li1.2Mn0.6Cr0.2Oz/ graphene anode material, i.e. x=0.62, y=0.08, wherein lithium manganese chromated oxide and stone
The mass ratio of black alkene is 100：1.
With lithium carbonate, manganese acetate, chromium acetate and graphene oxide are initiation material, by 1.471g manganese acetates and 0.458g second
Sour chromium is dissolved in 30mL H2The mixed solution of O and 20mL absolute ethyl alcohols；By graphene oxide ultrasonic disperse to wherein；By 0.466g
Lithium carbonate is dissolved in 100mL H2After O and pour into above-mentioned solution；The solution of gained is evaporated after 200 DEG C of dryings in 140 DEG C
10h；Dried presoma is loaded into crucible, is heated at being warmed up to 400 DEG C with the programming rate of 1 DEG C/min in batch-type furnace
3h；Finally it is transferred in tube furnace and is heat-treated 12h in 700 DEG C under Ar protections, it is i.e. available after furnace cooling
Li1.2Mn0.6Cr0.2Oz/ graphene anode material.
By above-mentioned Li1.2Mn0.6Cr0.2Oz/ graphene anode material carries out XRD tests, and its result is as shown in figure 1, from figure
Understand that the material of synthesis is spinelle and the composite of layered rock salt structure (R-3m).SEM test results such as Fig. 2 institutes of material
Show, it can be seen that the powder body material of synthesis is the self assembly ball combined by many microballoons, a small amount of flake graphite alkene interts
Wherein, the diameter of assembling ball is about 500nm.Tested using button cell, mixed powder, conductive carbon black and binding agent PVDF
The mass ratio of (Kynoar) is 8:1:1, metal lithium sheet is to pole, 1molL-1LiPF6/ EC+DMC (volume ratios 1：1) it is
Electrolyte, polypropylene material is barrier film, and battery test system is NEWARE TC53, and charging/discharging voltage window is 2.0~4.6V,
Charging and discharging currents density chooses 100 and 600 (3C) mAg respectively-1, the material as lithium ion battery positive pole when show it is good
Good chemical property.Button cell test result shows, in 100 and 600mAg-1Charging and discharging currents density under, put first
Electric specific capacity is respectively 231 and 210mAhg-1, as shown in Figure 3 and Figure 4；After 100 discharge and recharges, its specific discharge capacity
Respectively 233 and 205mAhg-1.High rate performance is tested as shown in figure 5, the material is under the multiplying power of 60C, its specific discharge capacity
Still up to 145mAhg-1。
Embodiment 2
Li1.2Mn0.5Cr0.3Oz/ graphene anode material, i.e. x=0.53, y=0.02, wherein lithium manganese chromated oxide and stone
The mass ratio of black alkene is 100：1.
With lithium carbonate, manganese acetate, chromium acetate and graphene oxide are initiation material, by 1.226g manganese acetates and 0.687g second
Sour chromium is dissolved in 30mL H2The mixed solution of O and 20mL absolute ethyl alcohols；By graphene oxide ultrasonic disperse to wherein；By 0.466g
Lithium carbonate is dissolved in 100mL H2After O and pour into above-mentioned solution；The solution of gained is evaporated after 200 DEG C of dryings in 140 DEG C
10h；Dried presoma is loaded into crucible, is heated at being warmed up to 400 DEG C with the programming rate of 1 DEG C/min in batch-type furnace
3h；Finally it is transferred in tube furnace and is heat-treated 12h in 700 DEG C under Ar protections, it is i.e. available after furnace cooling
Li1.2Mn0.5Cr0.3Oz/ graphene anode material.The XRD test results of material show that the material of synthesis is spinelle and stratiform
The composite of rock salt structure (R-3m).The SEM test results of material show that the powder body material of synthesis is self assembly ball, on a small quantity
Graphene is interspersed wherein, and the diameter for assembling ball is about 500nm.Tested using button cell, mixed powder, conductive carbon black and
The mass ratio of binding agent PVDF (Kynoar) is 8:1:1, metal lithium sheet is to pole, 1molL-1LiPF6/ EC+DMC (bodies
Product compares 1：1) it is electrolyte, polypropylene material is barrier film, and battery test system is NEWARE TC53, and charging/discharging voltage window is
2.0~4.6V, charging and discharging currents density chooses 100 and 600 (3C) mAg respectively-1, the material as lithium ion battery positive pole
When show good chemical property.Button cell test result shows, in 100 and 600mAg-1Charging and discharging currents it is close
Under degree, first discharge specific capacity is respectively 236 and 212mAhg-1；After 100 discharge and recharges, its specific discharge capacity difference
It is 231 and 203mAhg-1.High rate performance test shows that the material is under the multiplying power of 60C, and its specific discharge capacity is still reachable
148mAh·g-1。
Embodiment 3：Li1.3Mn0.5Cr0.2Oz/ graphene anode material, i.e. x=0.872, y=0.008, wherein lithium manganese chromium
The mass ratio of oxide and Graphene is 100：1.
With lithium carbonate, manganese acetate, chromium acetate and graphene oxide are initiation material, by 1.226g manganese acetates and 0.458g second
Sour chromium is dissolved in 30mL H2The mixed solution of O and 20mL absolute ethyl alcohols；By graphene oxide ultrasonic disperse to wherein；By 0.504g
Lithium carbonate is dissolved in 100mL H2After O and pour into above-mentioned solution；The solution of gained is evaporated after 200 DEG C of dryings in 140 DEG C
10h；Dried presoma is loaded into crucible, is heated at being warmed up to 400 DEG C with the programming rate of 1 DEG C/min in batch-type furnace
3h；Finally it is transferred in tube furnace and is heat-treated 12h in 700 DEG C under Ar protections, it is i.e. available after furnace cooling
Li1.3Mn0.5Cr0.2Oz/ graphene anode material.The XRD test results of material show that the material of synthesis is spinelle and stratiform
The composite of rock salt structure (R-3m).The SEM test results of material show that the powder body material of synthesis is self assembly ball, on a small quantity
Graphene is interspersed wherein, and the diameter for assembling ball is about 500nm.Tested using button cell, mixed powder, conductive carbon black and
The mass ratio of binding agent PVDF (Kynoar) is 8:1:1, metal lithium sheet is to pole, 1molL-1LiPF6/ EC+DMC (bodies
Product compares 1：1) it is electrolyte, polypropylene material is barrier film, and battery test system is NEWARE TC53, and charging/discharging voltage window is
2.0~4.6V, charging and discharging currents density chooses 100 and 600 (3C) mAg respectively-1, the material as lithium ion battery positive pole
When show good chemical property.Button cell test result shows, in 100 and 600mAg-1Charging and discharging currents it is close
Under degree, first discharge specific capacity is respectively 223 and 202mAhg-1；After 100 discharge and recharges, its specific discharge capacity difference
It is 229 and 201mAhg-1.High rate performance test shows that the material is under the multiplying power of 60C, and its specific discharge capacity is still reachable
134mAh·g-1。
Embodiment 4：Li1.3Mn0.4Cr0.3Oz/ graphene anode material, i.e. x=0.65, y=0.1, wherein lithium manganese chromium are aoxidized
The mass ratio of thing and Graphene is 100：1.
With lithium carbonate, manganese acetate, chromium acetate and graphene oxide are initiation material, by 0.981g manganese acetates and 0.687g second
Sour chromium is dissolved in 30mL H2The mixed solution of O and 20mL absolute ethyl alcohols；By graphene oxide ultrasonic disperse to wherein；By 0.504g
Lithium carbonate is dissolved in 100mL H2After O and pour into above-mentioned solution；The solution of gained is evaporated after 200 DEG C of dryings in 140 DEG C
10h；Dried presoma is loaded into crucible, is heated at being warmed up to 400 DEG C with the programming rate of 1 DEG C/min in batch-type furnace
3h；Finally it is transferred in tube furnace and is heat-treated 12h in 700 DEG C under Ar protections, it is i.e. available after furnace cooling
Li1.3Mn0.4Cr0.3Oz/ graphene anode material.The XRD test results of material show that the material of synthesis is spinelle and stratiform
The composite of rock salt structure (R-3m).The SEM test results of material show that the powder body material of synthesis is self assembly ball, on a small quantity
Graphene is interspersed wherein, and the diameter for assembling ball is about 500nm.Tested using button cell, mixed powder, conductive carbon black and
The mass ratio of binding agent PVDF (Kynoar) is 8:1:1, metal lithium sheet is to pole, 1molL-1LiPF6/ EC+DMC (bodies
Product compares 1：1) it is electrolyte, polypropylene material is barrier film, and battery test system is NEWARE TC53, and charging/discharging voltage window is
2.0~4.6V, charging and discharging currents density chooses 100 and 600 (3C) mAg respectively-1, the material as lithium ion battery positive pole
When show good chemical property.Button cell test result shows, in 100 and 600mAg-1Charging and discharging currents it is close
Under degree, first discharge specific capacity is respectively 233 and 208mAhg-1；After 100 discharge and recharges, its specific discharge capacity difference
It is 230 and 200mAhg-1.High rate performance test shows that the material is under the multiplying power of 60C, and its specific discharge capacity is still reachable
139mAh·g-1。
Embodiment 5
A kind of positive electrode, positive electrode includes spherical lithium manganese chromated oxide and is plugged in spherical lithium manganese chromated oxide
Between sheet Graphene, the molecular formula of the lithium manganese chromated oxide is Li1.14Mn0.57Cr0.29Oz, i.e. x=0.6, y=
0.2, the wherein mass ratio of lithium manganese chromated oxide and Graphene is 100：0.5.
The preparation method of above-mentioned positive electrode, comprises the following steps：
(1) it is in molar ratio 1.6：0.8:0.4 weighs lithium nitrate, manganese nitrate, chromic nitrate, and manganese nitrate and chromic nitrate are dissolved
In absolute ethyl alcohol, mixed solution is obtained, in Graphene ultrasonic disperse to mixed solution, will then add lithium nitrate dissolving,
Obtain precursor solution；
(2) precursor solution is evaporated at a temperature of 50 DEG C, 24h is dried at a temperature of 160 DEG C, then in Muffle furnace 300
Low Temperature Heat Treatment 24h is carried out under the conditions of DEG C, powder body material is obtained；
(3) powder body material is carried out into high-temperature heat treatment 24h under 600 DEG C, inert gas environment, cooling obtains final product the positive pole
Material.
After testing, the material as lithium ion battery positive pole when show good chemical property.
Embodiment 6
A kind of positive electrode, positive electrode includes spherical lithium manganese chromated oxide and is plugged in spherical lithium manganese chromated oxide
Between sheet Graphene, the molecular formula of the lithium manganese chromated oxide is Li1.08Mn0.58Cr0.34Oz, i.e. x=0.3, y=
0.0.01, wherein the mass ratio of lithium manganese chromated oxide and Graphene is 100：5.
The preparation method of above-mentioned positive electrode, comprises the following steps：
(1) it is in molar ratio 1.3：0.7:0.41 weighs lithium nitrate, manganese nitrate, chromic nitrate, and manganese nitrate and chromic nitrate is molten
Solution obtains mixed solution in absolute ethyl alcohol, by Graphene ultrasonic disperse to mixed solution, then adds lithium nitrate molten
Solution, obtains precursor solution；
(2) precursor solution is evaporated at a temperature of 160 DEG C, 3h is dried at a temperature of 250 DEG C, then in Muffle furnace 500
Low Temperature Heat Treatment 1h is carried out under the conditions of DEG C, powder body material is obtained；
(3) powder body material is carried out into high-temperature heat treatment 6h under 800 DEG C, inert gas environment, cooling obtains final product the positive pole
Material.
After testing, the material as lithium ion battery positive pole when show good chemical property.
Claims (8)
1. a kind of positive electrode, it is characterised in that the positive electrode includes spherical lithium manganese chromated oxide and is plugged in ball
The Graphene of the sheet between shape lithium manganese chromated oxide, the molecular formula of the lithium manganese chromated oxide is xLi2MO3·yLiM2O4·
(1-x-y)LiMO2, wherein, 0 ＜ x ＜, 1,0 ＜ y ＜ 1,0 ＜ 1-x-y ＜ 1, M represent Mn and/or Cr, the lithium manganese chromated oxide
It is 100 with the mass ratio of Graphene：(0.5~5).
2. a kind of positive electrode according to claim 1, it is characterised in that described 0.3≤x≤0.6,0.01≤y≤
0.2。
3. a kind of preparation method of positive electrode as claimed in claim 1 or 2, it is characterised in that methods described includes following several
Individual step：
(1) lithium salts, manganese salt, chromic salts and Graphene are weighed in proportion, manganese salt and chromic salts are dissolved, mixed solution is obtained, by graphite
In alkene ultrasonic disperse to mixed solution, lithium salts dissolving is then added, obtain precursor solution；
(2) precursor solution is evaporated, is dried, then carry out Low Temperature Heat Treatment, obtain powder body material；
(3) powder body material is carried out into high-temperature heat treatment under high temperature, inert gas environment, cooling obtains final product the positive electrode.
4. the preparation method of a kind of positive electrode according to claim 3, it is characterised in that described lithium salts is acetic acid
One or more in lithium, lithium nitrate, lithium chloride, lithium carbonate；The manganese salt is the one kind in manganese acetate, manganese nitrate, manganese chloride
Or it is several；The chromic salts is one or more in chromium acetate, chromic nitrate, chromium chloride.
5. the preparation method of a kind of positive electrode according to claim 3, it is characterised in that the manganese salt and chromic salts are dissolved in
In the mixed liquor of absolute ethyl alcohol or water or both.
6. the preparation method of a kind of positive electrode according to claim 3, it is characterised in that the precursor solution is evaporated
Temperature be 50 DEG C~160 DEG C, drying temperature be 160 DEG C~250 DEG C, 3~24h of drying time.
7. the preparation method of a kind of positive electrode according to claim 3, it is characterised in that the Low Temperature Heat Treatment is in horse
Not carried out in stove, treatment temperature is 300~500 DEG C, process time is 1~24h.
8. the preparation method of a kind of positive electrode according to claim 3, it is characterised in that the high-temperature heat treatment is in pipe
Carried out in formula stove, treatment temperature is 600~800 DEG C, 6~24h of process time.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102148372A (en) * | 2011-03-08 | 2011-08-10 | 中信国安盟固利动力科技有限公司 | Anode material of high-energy composite lithium-ion battery |
| CN103490046A (en) * | 2013-09-18 | 2014-01-01 | 中国科学院福建物质结构研究所 | Lithium-manganese-rich based solid solution/graphene composite material and preparation method thereof |
| CN104821390A (en) * | 2015-04-24 | 2015-08-05 | 中南大学 | Lithium manganese borate/graphene as cathode materials for lithium-ion batteries and preparation method of lithium manganese borate / graphene |
-
2016
- 2016-12-28 CN CN201611233185.6A patent/CN106856238A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102148372A (en) * | 2011-03-08 | 2011-08-10 | 中信国安盟固利动力科技有限公司 | Anode material of high-energy composite lithium-ion battery |
| CN103490046A (en) * | 2013-09-18 | 2014-01-01 | 中国科学院福建物质结构研究所 | Lithium-manganese-rich based solid solution/graphene composite material and preparation method thereof |
| CN104821390A (en) * | 2015-04-24 | 2015-08-05 | 中南大学 | Lithium manganese borate/graphene as cathode materials for lithium-ion batteries and preparation method of lithium manganese borate / graphene |
Non-Patent Citations (1)
| Title |
|---|
| DONG LUO等: "A New Spinel-Layered Li-Rich Microsphere as a High-Rate Cathode Material for Li-Ion Batteries", 《ADVANCED ENERGY MATERIALS》 * |
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