CN108264090A - A kind of non-electrochemical activates Li2MnO3Method - Google Patents

A kind of non-electrochemical activates Li2MnO3Method Download PDF

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Publication number
CN108264090A
CN108264090A CN201810049663.0A CN201810049663A CN108264090A CN 108264090 A CN108264090 A CN 108264090A CN 201810049663 A CN201810049663 A CN 201810049663A CN 108264090 A CN108264090 A CN 108264090A
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mno
electrochemical
heat treatment
activates
activation
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张友祥
马晓玲
孙亚
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Lin Li (wuhan) Amperex Technology Ltd
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Lin Li (wuhan) Amperex Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of non-electrochemicals to activate Li2MnO3Method, belong to technical field of inorganic material.The method includes：By Li2MnO3It is uniform with solid state reduction material mixing, solvent is added in, grinds and is adjusted to rheological body；Rheological body is placed in inert atmosphere and carries out the first heat treatment postcooling to room temperature；By the Li after the first heat treatment2MnO3It is cleaned；By the Li after over cleaning2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling to room temperature, Li2MnO3Activation is completed.Pass through the Li after the method activation of the present invention2MnO3Material has electro-chemical activity, when as anode material for lithium-ion batteries, without being activated again by electrochemical method, with non-activated Li2MnO3Material is compared, the Li after being activated by this chemical method2MnO3Material has better chemical property, and the coulombic efficiency of first run charge and discharge is high, and specific capacity is high, good cycle.

Description

A kind of non-electrochemical activates Li2MnO3Method
Technical field
The present invention relates to technical field of inorganic material, more particularly to a kind of non-electrochemical activation Li2MnO3Method.
Background technology
Commercialized anode material for lithium-ion batteries mainly has cobalt acid lithium (LiCoO2), ternary material (such as LiNi1-x- yCoxMnyO2) and LiFePO4 (LiFePO4)。LiCoO2It is expensive, toxicity is big, safety is poor, actual specific capacity is not high (about 140mAh/g)；LiFePO4It is nontoxic, pollution-free, safety is good, cheap, but its theoretical specific capacity only has 170mAh/g；Three First material LiNi1-x-yCoxMnyO2For the material of currently Devoting Major Efforts To Developing application, but wherein similary contain expensive and toxic Co Element, and safety is still to be improved.At present, it is lithium ion to find with more height ratio capacity, safer cheap positive electrode One of research hotspot of field of batteries.Stratiform lithium-rich anode material xLi2MnO3·(1-x)LiMO2(M=Ni, Co, Mn；0≤x≤ 1) due to containing a certain amount of lithium in the transition metal layer of crystal structure, the specific capacity of material it is high (up to~ 300mAh/g).Meanwhile xLi2MnO3·(1-x)LiMO2Li in (M=Ni, Co, Mn) material2MnO3Component can play stabilization LiMO2The effect of layer structure allows the depth that rich lithium type positive electrode realizes lithium ion to deviate from without structure is caused to be collapsed It collapses；LiMO2Can then play in turn improves Li2MnO3The effect of cycle performance, so that lithium-rich anode material specific capacity It is high, at low cost and have preferable safety.
Li2MnO3It is a terminal material xLi of stratiform lithium-rich anode material2MnO3·(1-x)LiMO2(x=1), material In containing only Mn, without toxic Elements C o and more rare element Ni, element M n is nontoxic, and the content in the earth's crust is high, and resource is rich Richness, thus it is cheap；In addition, due to containing in a molecule, there are two lithium ion, Li2MnO3Theoretical specific capacity be up to 459mAh/g is a urgently ideal lithium leaved for development higher than any anode material for lithium-ion batteries in being currently being deployed Electric positive electrode.But with other lithium manganese oxides (LiMnO2And LiMn2O4) unlike, Li2MnO3In all Mn be all+4 Valency can not be further oxided, therefore in usually used battery voltage range (2.0~4.4V), Li2MnO3There is no electricity Chemism.
In order to make Li2MnO3With electro-chemical activity, at present the common way of industry be using electrochemical method by material into Row activation, specific practice are：By Li2MnO3It charges, in charging process, expands the voltage range of charging, at high voltage (at least 4.5V vs.Li+/Li)Li2MnO3Oxonium ion O in crystal2-It is oxidized to O-Ion or O atom or O2Molecule.It is this Electrochemical activation, which is showed, to be characterized in Li2MnO3In the first charge-discharge curve of material, the (~4.5V at high voltage vs.Li+/ Li) there are one very long significant charging voltage platforms.In addition, during electrochemical activation, with O2Disengage and The lithium ion Li of abjection+Return to Li with being not effectively reversible2MnO3In, therefore, electrochemical activation Li2MnO3It is caused certainty consequence be Li2MnO3Material coulombic efficiency in first run charge and discharge cycles is very low.
Invention content
The present invention activates Li by providing a kind of non-electrochemical2MnO3Method, solve and activated using electrochemical method Li2MnO3Lead to Li2MnO3Material the technical issues of coulombic efficiency is low in first run charge and discharge cycles.
In order to solve the above technical problems, the present invention provides a kind of non-electrochemicals to activate Li2MnO3Method, the method Including：
By Li2MnO3It is uniform with solid state reduction material mixing, solvent is added in, grinds and is adjusted to rheological body；
The rheological body is placed in inert atmosphere and carries out the first heat treatment postcooling to room temperature；
By the Li after the described first heat treatment2MnO3It is cleaned；
By the Li after the cleaning2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling to room temperature, Li2MnO3Activation is completed.
Further, the Li2MnO3Molar ratio with solid state reduction substance is 1:0.01~0.1.
Further, the solid state reduction substance is carbon black, activated carbon, graphite, graphene, carbon nanotube, poly- second two Any one in alcohol or aliphatic acid.
Further, the solvent is water, alcohols or ketones solvent.
Further, the temperature of first heat treatment is 300-400 DEG C, time 1-10h.
Further, the temperature of second heat treatment is 100-400 DEG C, time 1-10h.
Further, the cleaning is successively cleaned with water and ethyl alcohol.
Further, the inert atmosphere includes nitrogen, argon gas or helium.
Further, hydrogen is further included in the inert atmosphere of the first heat treatment.
One or more of the embodiment of the present application technical solution, has at least the following technical effects or advantages：
1st, non-electrochemical activation Li provided by the embodiments of the present application2MnO3Method, including：By Li2MnO3With solid state reduction Property material mixing it is uniform, add in solvent, grind and be adjusted to rheological body；The rheological body is placed in inert atmosphere and carries out the first heat Postcooling is handled to room temperature；By the Li after the described first heat treatment2MnO3It is cleaned；It will be after the cleaning Li2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling to room temperature, Li2MnO3Activation is completed.Pass through chemical method pair Li2MnO3It is activated, solves electrochemical method activation Li2MnO3Lead to Li2MnO3Material library in first run charge and discharge cycles The technical issues of human relations efficiency is low, the Li after activation2MnO3Material has better chemical property, the coulombic efficiency of first run charge and discharge Height, specific capacity is high, good cycle.
2nd, non-electrochemical activation Li provided by the embodiments of the present application2MnO3Method, easy to operate without special installation, item Part is easily-controllable, suitable for large-scale industrial production.
Description of the drawings
Fig. 1 is the embodiment of the present application non-electrochemical activation Li2MnO3Method flow diagram；
Fig. 2 is charging and discharging curve of 1 product of the embodiment of the present application under the current density of 30mA/g
Fig. 3 is charging and discharging curve of 2 product of the embodiment of the present application under the current density of 30mA/g；
Fig. 4 is charging and discharging curve of 3 product of the embodiment of the present application under the current density of 30mA/g；
Fig. 5 is charging and discharging curve of 4 product of the embodiment of the present application under the current density of 30mA/g.
Specific embodiment
The embodiment of the present application provides a kind of non-electrochemical activation Li2MnO3Method, solve and activated using electrochemical method Li2MnO3Lead to Li2MnO3Material the technical issues of coulombic efficiency is low in first run charge and discharge cycles, after being activated using this method Li2MnO3With better chemical property, recycle including higher coulombic efficiency, better high rate capability and preferably Performance.
In order to solve the above technical problems, the embodiment of the present application general thought is as follows：
This application provides a kind of non-electrochemicals to activate Li2MnO3Method, including：
By Li2MnO3It is uniform with solid state reduction material mixing, solvent is added in, grinds and is adjusted to rheological body；
The rheological body is placed in inert atmosphere and carries out the first heat treatment postcooling to room temperature；
By the Li after the described first heat treatment2MnO3It is cleaned；
By the Li after the cleaning2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling to room temperature, Li2MnO3Activation is completed.
Above-mentioned technical proposal, due to using chemical method to Li2MnO3It is activated, solves electrochemical method activation Li2MnO3Lead to Li2MnO3Material the technical issues of coulombic efficiency is low in first run charge and discharge cycles, achieve first run charge and discharge Recycle the technique effect of efficient coulomb, high rate capability and good cycle.
In order to better understand the above technical scheme, technical scheme is done below by the drawings and specific embodiments Detailed description, it should be understood that the specific features in the embodiment of the present application and embodiment are to the detailed of technical scheme Explanation rather than restriction to technical scheme, in the absence of conflict, in the embodiment of the present application and embodiment Technical characteristic can be combined with each other.
The embodiment of the present application provides a kind of non-electrochemical activation Li2MnO3Method, as shown in Figure 1, including following step Suddenly：
Step S110：By Li2MnO3It is uniform with solid state reduction material mixing, solvent is added in, grinds and is adjusted to rheological body；
In the step, the solid state reduction substance is carbon black, activated carbon, graphite, graphene, carbon nanotube, poly- second two Any one in alcohol or aliphatic acid.Turned when the relative molecular mass of polyethylene glycol and aliphatic acid increases to a certain extent by liquid Become solid-state, the relative molecular mass range of choice of polyethylene glycol and aliphatic acid meets it in solid-state.Solid state reduction object Matter plays reduction, makes Li2MnO3Lacking oxygen is generated in crystal.
In the step, the Li2MnO3Molar ratio with solid state reduction substance is 1:0.01~0.1.Li2MnO3With consolidating The molar ratio of state reducing substances is no more than 1:0.1, if more than 1:0.1, then Li2MnO3The Lacking oxygen generated in crystal is too many, Material crystal structure can change, and qualitative change occurs for material, is no longer Li2MnO3And it is transformed into another material.
In the step, the solvent is water, alcohols or ketones solvent.If the solid state reduction substance used is carbon black, work When property charcoal, graphite, graphene, carbon nanotube or all kinds of aliphatic acid, alcohols or ketones solvent are used；If the solid state reduction used When substance is the polyethylene glycol of high molecular weight, using water as solvent.Solvent adding amount makes Li2MnO3With solid state reduction substance It is advisable after mixed grinding in rheological body, rheological body is the material for having rheological property, and material has elasticity, viscosity, can be at any time Deformation, becomes creep or flowable state.
Step S120：The rheological body is placed in inert atmosphere and carries out the first heat treatment postcooling to room temperature；
In this step, the temperature of first heat treatment is 300-400 DEG C, time 1-10h.Carry out the first heat treatment Purpose is that material crystals is made to generate Lacking oxygen, and suitable temperature and time is necessary, and temperature is too low, the time is too short, activates effect Fruit unobvious；Temperature is excessively high, overlong time then activates excessively, and qualitative change occurs for material, is no longer Li2MnO3。
Here, any one in the inert atmosphere selection nitrogen, argon gas or helium.Further, the nitrogen, argon gas or It may also include a small amount of hydrogen in helium.The effect of activation can be played by adding in a small amount of hydrogen, become apparent from activation effect, hydrogen adds Entering amount should not be excessive, general addition in 5% (volume) below.If first time thermal effectiveness is apparent, without hydrogenation, If first time thermal effectiveness is undesirable, a small amount of hydrogen can be added in an inert atmosphere.
Step S130：By the Li after the described first heat treatment2MnO3It is cleaned；
In this step, the cleaning is specifically successively to be cleaned with water and ethyl alcohol, and reaching removal, heat treatment generates for the first time By-product purpose.
Step S140：By the Li after the cleaning2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling extremely Room temperature, Li2MnO3Activation is completed.
In this step, the temperature of second heat treatment is 100-400 DEG C, time 1-10h.Carry out the second heat treatment Purpose is removal moisture content, temperature and time is too low can cause it is dry insufficient, it is excessively high, cause energy dissipation.
Here, any one in the inert atmosphere selection nitrogen, argon gas or helium.
Above-mentioned activation method using chemical method rather than electrochemical method, makes Li2MnO3Material obtains electro-chemical activity, Li after being activated using this chemical method2MnO3Material is when as anode material for lithium-ion batteries, without reusing electrochemistry Method activates material.With non-activated Li2MnO3Material is compared, and during using identical charging/discharging voltage window, uses this chemistry Li after method activation2MnO3Material is not in charging voltage platform at high voltage, and first run charge and discharge coulombic efficiency has It significantly improves.In addition, the activation method is simple, condition is easily-controllable, suitable for industrialized production.
In order to which those skilled in the art is enable further to understand the scheme of the embodiment of the present invention, will be based below The scheme that the embodiment of the present application is introduced describes to it in detail.
Embodiment 1
Weigh 0.1757g Li2MnO3With 0.0167g carbon nanotubes, by Li2MnO3It is uniformly mixed with carbon nanotube, then 0.9mL isopropyl acetones are added in into mixture, mixture is adjusted to rheological body in 10 minutes by grinding.Then, by the rheological body side of being transferred to Boat is calcined 5 hours, cooled to room temperature later in 350 DEG C under an argon atmosphere.By Li after cooling2MnO3Successively spend from Sub- water and washes of absolute alcohol, it is then 10 hours dry at 100 DEG C under argon gas atmosphere.By products therefrom with it is not processed Li2MnO3Simulated battery is assembled into as positive electrode, electrochemistry is carried out under new prestige (Shenzhen) high accuracy battery test system It can test.Obtained material first run charging and discharging curve such as attached drawing 2, the finger that " unactivated " is designated as in figure be not processed Li2MnO3, be designated as " after activation " be the present embodiment activation products.It can be seen from Fig. 2 that non-activated Li2MnO3First charge-discharge In cycle, charge specific capacity 181.96mAh/g, specific discharge capacity 61.22mAh/g, coulombic efficiency 33.64%；Activation Li afterwards2MnO3In first charge-discharge cycle, charge specific capacity 129.68mAh/g, specific discharge capacity 104.89mAh/g, library Human relations efficiency is 80.88%.It is handled by chemical activation, the coulombic efficiency of first run charge and discharge cycles is improved extremely by 33.64% 80.88%.
Embodiment 2
Weigh 0.1757g Li2MnO3With 0.0239g polyethylene glycol (molecular weight：10000), by Li2MnO3And polyethylene glycol It is uniformly mixed, 0.5mL deionized waters is then added in into mixture, mixture is adjusted to rheological body in 10 minutes by grinding.Then, will Rheological body is transferred to Noah's ark, is calcined 10 hours in 300 DEG C under an argon atmosphere, cooled to room temperature later.It will be after cooling Li2MnO3Priority deionized water and washes of absolute alcohol, it is then 6 hours dry at 200 DEG C under argon gas atmosphere.Gained is produced Object and no processed Li2MnO3Simulated battery is assembled into as positive electrode, system is tested in new prestige (Shenzhen) high accuracy battery System is lower to carry out electrochemical property test.Obtained material first run charging and discharging curve such as attached drawing 3 is designated as the finger of " unactivated " in figure There is no processed Li2MnO3, be designated as " after activation " be the present embodiment activation products.It is it can be seen from Fig. 3 that non-activated Li2MnO3In first charge-discharge cycle, charge specific capacity 181.96mAh/g, specific discharge capacity 61.22mAh/g, coulomb effect Rate is 33.64%；Li after activation2MnO3In first charge-discharge cycle, charge specific capacity 140.22mAh/g, specific discharge capacity For 120.48mAh/g, coulombic efficiency 85.92%.Handled by chemical activation, the coulombic efficiencies of first run charge and discharge cycles by 33.64% improves to 85.92%.
Embodiment 3
Weigh 0.2335g Li2MnO3With 0.0173g stearic acid, by Li2MnO3It is uniformly mixed with stearic acid, then to mixed It closes and 0.5mL absolute ethyl alcohols is added in object, mixture is adjusted to rheological body in 10 minutes by grinding.Then, rheological body is transferred to Noah's ark, It is calcined 6 hours in 380 DEG C in a nitrogen atmosphere, cooled to room temperature later.By Li after cooling2MnO3Priority deionization Water and washes of absolute alcohol, it is then 1 hour dry at 400 DEG C under nitrogen atmosphere.By products therefrom with it is not processed Li2MnO3Simulated battery is assembled into as positive electrode, electrochemistry is carried out under new prestige (Shenzhen) high accuracy battery test system It can test.Obtained chemical property figure such as attached drawing 4 is designated as the no processed Li of finger of " unactivated " in figure2MnO3, mark For " after activation " be the present embodiment activation products.It can be seen from Fig. 4 that non-activated Li2MnO3In first charge-discharge cycle, fill Electric specific capacity be 181.96mAh/g, specific discharge capacity 61.22mAh/g, coulombic efficiency 33.64%；Li after activation2MnO3 In first charge-discharge cycle, charge specific capacity 182.84mAh/g, specific discharge capacity 153.92mAh/g, coulombic efficiency is 84.18%.It is handled by chemical activation, the coulombic efficiency of first run charge and discharge cycles is improved by 33.64% to 84.18%.
Embodiment 4
Weigh 0.2335g Li2MnO3With 0.0229g stearic acid, by Li2MnO3It is uniformly mixed with stearic acid, then to mixed It closes and 0.9mL absolute ethyl alcohols is added in object, mixture is adjusted to rheological body in 10 minutes by grinding.Then, rheological body is transferred to Noah's ark, It is calcined 1 hour in 400 DEG C under an argon atmosphere, cooled to room temperature later.By Li after cooling2MnO3Priority deionization Water and washes of absolute alcohol, it is then 4 hours dry at 300 DEG C under argon gas atmosphere.By products therefrom with it is not processed Li2MnO3Simulated battery is assembled into as positive electrode, electrochemistry is carried out under new prestige (Shenzhen) high accuracy battery test system It can test.Obtained chemical property figure such as attached drawing 5 is designated as the no processed Li of finger of " unactivated " in figure2MnO3, mark For " after activation " be the present embodiment activation products.It can be seen from Fig. 5 that non-activated Li2MnO3In first charge-discharge cycle, fill Electric specific capacity be 181.96mAh/g, specific discharge capacity 61.22mAh/g, coulombic efficiency 33.64%；Li after activation2MnO3 In first charge-discharge cycle, charge specific capacity 150.87mAh/g, specific discharge capacity 126.43mAh/g, coulombic efficiency is 83.80%.It is handled by chemical activation, the coulombic efficiency of first run charge and discharge cycles is improved by 33.64% to 83.80%.
It should be noted last that more than specific embodiment is merely illustrative of the technical solution of the present invention and unrestricted, Although the present invention is described in detail with reference to example, it will be understood by those of ordinary skill in the art that, it can be to the present invention Technical solution be modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention, should all cover In scope of the presently claimed invention.

Claims (9)

1. a kind of non-electrochemical activates Li2MnO3Method, which is characterized in that the method includes：
By Li2MnO3It is uniform with solid state reduction material mixing, solvent is added in, grinds and is adjusted to rheological body；
The rheological body is placed in inert atmosphere and carries out the first heat treatment postcooling to room temperature；
By the Li after the described first heat treatment2MnO3It is cleaned；
By the Li after the cleaning2MnO3It is placed in inert atmosphere and carries out the second heat treatment postcooling to room temperature, Li2MnO3It is living Change and complete.
2. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that the Li2MnO3With solid-state also The molar ratio of immunogenic substance is 1:0.01~0.1.
3. non-electrochemical as claimed in claim 1 or 2 activates Li2MnO3Method, which is characterized in that the solid state reduction Substance is any one in carbon black, activated carbon, graphite, graphene, carbon nanotube, polyethylene glycol or aliphatic acid.
4. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that the solvent for water, alcohols Or ketones solvent.
5. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that it is described first heat treatment temperature It spends for 300-400 DEG C, time 1-10h.
6. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that it is described second heat treatment temperature It spends for 100-400 DEG C, time 1-10h.
7. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that it is described cleaning priority water with Ethyl alcohol cleans.
8. non-electrochemical as described in claim 1 activates Li2MnO3Method, which is characterized in that the inert atmosphere include nitrogen Gas, argon gas or helium.
9. non-electrochemical as claimed in claim 8 activates Li2MnO3Method, which is characterized in that first heat treatment described in Hydrogen is further included in inert atmosphere.
CN201810049663.0A 2018-01-18 2018-01-18 A kind of non-electrochemical activates Li2MnO3Method Pending CN108264090A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112897584A (en) * 2021-01-21 2021-06-04 湘潭大学 Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107293742A (en) * 2017-07-25 2017-10-24 黄冈林立新能源科技有限公司 A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107293742A (en) * 2017-07-25 2017-10-24 黄冈林立新能源科技有限公司 A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112897584A (en) * 2021-01-21 2021-06-04 湘潭大学 Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof

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Application publication date: 20180710