CN102244256A - Cathode active material with core shell structure, preparation method and secondary battery using material - Google Patents

Cathode active material with core shell structure, preparation method and secondary battery using material Download PDF

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CN102244256A
CN102244256A CN2011101505264A CN201110150526A CN102244256A CN 102244256 A CN102244256 A CN 102244256A CN 2011101505264 A CN2011101505264 A CN 2011101505264A CN 201110150526 A CN201110150526 A CN 201110150526A CN 102244256 A CN102244256 A CN 102244256A
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active material
solution
cathode
lithium
soluble
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宋文娥
谢娇娜
王雅和
吴宁宁
刘建红
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RiseSun MGL New Energy Technology Co Ltd
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CITIC Guoan Mengguli Power Technology Co Ltd
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Abstract

The invention discloses a cathode active material with a core shell structure, a preparation method and a secondary battery using the cathode active material, belonging to the technical field of secondary battery cathode active materials and preparation thereof. The general formula of the cathode active material with the core shell structure is mLiMn2-xMxO4.(1-m)Li1+yMn1-y-zM'zO2, wherein x is larger than or equal to 0 and smaller than or equal to 1, y is larger than or equal to 0 and smaller than or equal to 1/3, z is larger than or equal to 0 and smaller than 1, and m is larger than 0 and smaller than 1. The active material takes a spinel structure LiMn2-xMxO4 as a core and lamellar Li1+yMn1-y-zM'zO2 as a shell. The material has low raw material cost and simple synthetic process. The preparation method mainly comprises the preparation of a precursor and the synthesis of a polycrystalline solid. The liquid coprecipitation method is adopted in the precursor preparation so that all elements are mixed on an atom level, and the obtained product is uniform. The material has good processability, and the secondary battery assembled by using the material has excellent cycle performance.

Description

A kind of nucleocapsid structure active material of cathode, preparation method and use the secondary cell of this material
Technical field
The invention belongs to secondary cell active material of cathode and preparing technical field thereof, particularly a kind of nucleocapsid structure active material of cathode and preparation method, and the secondary cell of using this active material of cathode.
Background technology
Swift and violent increase and the jumbo lithium ion battery of electric automobile needs along with the lithium ion battery consumption press for development and have high safety, high-energy-density, high power, long circulation, high environmental protection and inexpensive lithium ion battery.
LiMn 2-xM xO 4Material has the three-dimensional tunnel structure of spinel serial material uniqueness, is suitable for high current charge-discharge; Therefore its abundant raw material and price is relatively cheap, and safety non-pollution are considered to one of battery material that has the applications well prospect, especially in electric tool, electric motor car etc. to fail safe and the higher application of cost requirement.But also there are some defectives in this material: its high temperature circulation poor stability, and the serious problem of high temperature capacity attenuation also is not well solved, and its capacity is lower, and theoretical specific capacity is 148mAh/g.
Stratiform Li 1+yMn 1-y-zM ' zO 2Material is owing to having the focus that higher specific capacity (greater than 200mAh/g), excellent normal temperature and high temperature circulation ability become research.Itself and common stratiform active material of cathode such as LiCoO 2Compare, in transition metal layer, contain a certain amount of lithium, therefore be also referred to as rich lithium material.Li 1+yMn 1-y-zM ' zO 2Molecular formula also can be rewritten as 2y/ (1-y) Li 2MnO 3[(1-3y)/(1-y)] Li[Mn (1-3y-z)M ' z] 1/ (1-3y)O 2Form, Li 2MnO 3In the compound, manganese does not have activity for+4 valencys, valence state does not take place in charge and discharge process change, and makes that the structure of material is stablized.Wu etc. find the Li[Li that coprecipitation method is synthetic 0.2Mn 0.54Ni 0.13Co 0.13] O 2The first discharge specific capacity of material under the C/20 current ratio is 253mAh/g, when the first discharge specific capacity during 2C only is C/20 69.2%, the high rate performance of material remains to be improved (Electrochemical and Solid State Letters, 9, (2006): A221).
LiMn 2-xM xO 4Material and Li 1+yMn 1-y-zM ' zO 2Material all is a manganese base active material of cathode, has characteristics such as nontoxic, pollution-free, raw material wide material sources, low price, but also has shortcoming separately; For the rich Li material of the multiplying power discharging property that spinel is good and stratiform excellent cycle performance mutually combines, and overcome shortcoming separately, we have synthesized the cathode activity composite material of nucleocapsid structure, and use it for the preparation lithium rechargeable battery.
Summary of the invention
The object of the present invention is to provide a kind of nucleocapsid structure lithium ion battery active material of cathode and preparation method thereof, obtain a kind of energy density height, have extended cycle life, the lithium ion active material of cathode that voltage range is big, high temperature cyclic performance is good.
Nucleocapsid structure active material of cathode provided by the invention, its composition general formula is: mLiMn 2-xM xO 4(1-m) Li 1+yMn 1-y-zM ' zO 2, 0≤x≤1,0≤y≤1/3,0≤z＜1,0＜m＜1 wherein, this material is with spinel structure LiMn 2-xM xO 4For nuclear, with stratiform Li 1+yMn 1-y-zM ' zO 2Be shell, M and M ' are one or more among Ni, Mg, Cu, Co, Zn, Cr, Fe, the Zr.
Stratiform Li 1+yMn 1-y-zM ' zO 2Can be LiMnO 2, LiNi 0.5Mn 0.5O 2, Li (Li 1/3Mn 2/3) O 2Deng crystal structure; Z is not 0 o'clock, M ' preferred Ni, Ni and Co, such as: Li (Li yNi zMn 1-y-z) O 2, Li (Li yNi Z-aMn 1-y-zCo a) O 2Deng crystal structure, 0≤y≤1/3,0≤z＜1,0≤a＜1 wherein.
The present invention also provides a kind of preparation method of nucleocapsid structure active material of cathode, and this method comprises the steps:
1) soluble-salt of soluble manganese salt and M is pressed Mn: the mol ratio of M is (2-x): x, wherein to be mixed with concentration of metal ions be 0.5-3.0mol/L (preferred 1.0～2.5mol/L to the ratio of 0≤x≤1 (preferred 0～0.5), more excellent 2.0mol/L) soluble salt mixed solution I, wherein M is one or more among Ni, Mg, Cu, Co, Zn, Cr, Fe, the Zr;
2) soluble-salt of soluble manganese salt and M ' is pressed Mn: the mol ratio of M ' is (1-y-z): z, wherein 0≤y≤1/3 (preferred 0～0.2), it is 0.5～3.0mol/L (preferred 1.0～2.5mol/L that the ratio of 0≤z＜1 (preferred 0～0.5) is mixed with concentration of metal ions, more excellent 2.0mol/L) soluble salt mixed solution I I, wherein M ' is one or more among Ni, Mg, Cu, Co, Zn, Cr, Fe, the Zr;
3) obtain solution III, solution III is an alkaline aqueous solution, the mixed solution that described alkaline aqueous solution selects for use sodium hydroxide solution or NaOH and ammoniacal liquor to form, the sodium hydroxide solution of preferred ammoniacal liquor and 1.0-4.0mol/L is 1 by volume: the mixed solution that ratio (5-15) is mixed with;
4) above-mentioned soluble salt mixed solution I and solution III are evenly joined in the reactor simultaneously continuously react, the ph value of control reaction is 9～11 (preferred 10.0), reaction temperature is 40～60 ℃ (preferred 55 ℃), stir in the time of reaction, the reinforced back of finishing continues to stir 0.5～5 hour, obtain intermediate material, continue to add soluble salt mixed solution I I and solution III, the control reaction pH value is 9～11, reaction temperature is 40～60 ℃, stirs in the time of reaction, and the reinforced back of finishing continues to stir 0.5～5 hour, obtain mixed material, wherein control the ratio of nucleocapsid by the consumption of control soluble salt mixed solution I and soluble salt mixed solution I I;
5) the said mixture material is carried out suction filtration, use deionized water wash, drying to obtain sphere or the spherical presoma of class then;
6) above-mentioned presoma and lithium salts is even by the molecular formula mixed, can directly mix, perhaps in the mixed solution of deionized water, absolute ethyl alcohol or deionized water and absolute ethyl alcohol, mix, obtain drying composite after the drying;
7) with the mixture in the above-mentioned steps under 400～600 ℃ of temperature constant temperature 0.5-10 hour, ground the cooling back, calcining at constant temperature 5～20 hours under 800～1000 ℃ of temperature again, and cooling, pulverizing, screening, classification obtain final products.
Lithium salts of the present invention is at least a in lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, the lithium fluoride.
The soluble-salt of the M that the present invention relates to is one or more in the chloride, fluoride, iodide, sulfate, nitrate, acetate, oxalates of M; The soluble-salt of M ' is one or more in the chloride, fluoride, iodide, sulfate, nitrate, acetate, oxalates of M '.
The negative electrode that nucleocapsid structure active material of cathode of the present invention is prepared from.
A kind of lithium rechargeable battery comprises above-mentioned negative electrode, anode and electrolyte.
This active material of cathode can be used for following secondary cell.
Fig. 5 shows the secondary cell profile that uses this active material of cathode according to embodiment of the present invention.This secondary cell is so-called button secondary cell, comprises plate-like cathode 2 that is included in the package casing 1 and the sheet anode 4 that is included in the cap 3, and barrier film 5 is between negative electrode 2 and the anode 4.Fill with electrolyte solution 6 inside of package casing 1 and cap 3, and electrolyte 6 is a liquid electrolyte, and the peripheral part of package casing 1 and cap 3 seals with insulated ring 7.
Package casing 1 and cap 3 materials are stainless steel.Package casing 1 plays the effect of the current collector body of negative electrode 2, and cap 3 plays the effect of the current collector body of anode 4.
Negative electrode 2 comprises according to active material of cathode provided by the invention, it with carbon black or electrically conductive graphite (making conductive agent) and Kynoar (making bonding agent) as cathode material.For example, mix active material of cathode, conductive agent and bonding agent, this cathode mix is compression molded into sheet, form negative electrode 2 with after the preparation cathode mix.In addition, except active material of cathode, electric conductor and adhesive directly prepare negative electrode 2 these methods, can also add for example N-methyl pyrrolidone (NMP) of mixed solvent, with the preparation cathode mix, make after this cathode mix drying, can this cathode mix of pressing mold so that form negative electrode 2.Yet, when this active material of cathode contact water, can weaken its function, the active material of cathode of therefore preferred bone dry as active material of cathode.
Anode 4 comprises from lithium metal, lithium alloy and can embed and deviate from the group that the material of lithium constitutes selects a kind of or two kinds or more of materials.The material that can embed and deviate from lithium comprises carbonaceous material, metallic compound, silicon, silicon compound and conducting polymer, and uses a kind of, two or more the mixture of selecting from them.For example as carbonaceous material, but graphite, agraphitic carbon graphitized carbon etc. are arranged; As metallic compound, SnO for example 2, SiC.Wherein, preferred carbonaceous material.When using the active material of positive electrode of powder type, anode 4 comprises the material that uses with the Kynoar that uses as adhesive.In this case, after multilayer anode active material and adhesive are with the preparation anode mixture, resulting anode mixture is compression molded into sheet, so that form anode 4., except the material and adhesive that can embed and deviate from lithium, can add solvent such as N-methyl pyrrolidone herein, with the preparation anode mixture, and after dry anode mixture, can this anode mixture of pressing mold, so that form anode 4.
Barrier film 5 is isolated negative electrode 2 and anode 4, with the short circuit current that prevents to cause owing to the contact between negative electrode 2 and the anode 4, and provides the passage that can allow lithium ion pass through.Barrier film 5 is for example made by perforated membrane, and this perforated membrane is made of synthetic resin such as polytetrafluoroethylene, polypropylene or polyethylene.Barrier film 5 can have wherein the structure of the two kinds or more of laminations that will select in the perforated membrane.
Form electrolyte solution 6 by dissolving lithium salts in solvent, and this electrolyte solution 6 shows ionic conductivity by the ionization of lithium salts in solvent.As lithium salts, LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiCF 3SO 3, LiN (CF 3SO 2) 2Deng all is suitable, can select the mixture of a kind of salt or two or more salt during use from them.
As solvent, anhydrous organic solvent for example propene carbonate, ethylene carbonate, methyl ethyl carbonate, butylene, vinylene carbonate, r-butyrolactone, sulfolane, methyl propionate, methyl butyrate, dimethyl carbonate, diethyl carbonate or dipropyl carbonate is preferred, a kind of solvent that use is selected from them or the mixture of two or more solvents.
Because active material of cathode is for comprising stratiform Li 1+yMn 1-y-zM ' zO 2The material of high-energy-density, therefore the secondary lithium battery that obtains has higher energy density.
Nucleocapsid structure active material of cathode cost of material provided by the invention is lower, synthesis technique is simple, mainly comprises the preparation of presoma and the sintering process of polycrystalline solid phase powder body material.Liquid-phase coprecipitation is adopted in the presoma preparation, and each element is mixed on atomic level, and products therefrom is even, and gained materials processing is functional.
The electrokinetic cell that adopts active material of cathode provided by the invention to prepare can be widely used in the energy-storage system of industries such as electric automobile, bicycle and wind-powered electricity generation, nuclear power, solar energy, intelligent grid peak regulation.
Description of drawings
Fig. 1 is the SEM figure of embodiment 1;
Fig. 2 is the lithium rechargeable battery charging and discharging curve figure of the assembling of embodiment 1;
Fig. 3 is the SEM figure of embodiment 2;
Fig. 4 is the lithium rechargeable battery cycle performance figure of the assembling of embodiment 2;
Fig. 5 is for using the secondary cell profile of active material of cathode of the present invention.
Number in the figure: 1-package casing; The 2-negative electrode; The 3-cap; The 4-anode; The 5-barrier film; The 6-electrolyte solution; 7 insulated rings.
Embodiment
Below in conjunction with drawings and Examples the present invention is further specified.Nucleocapsid structure lithium ion battery active material of cathode general formula of the present invention is mLiMn 2-xM xO 4(1-m) Li 1+yMn 1-y-zM ' zO 2, 0≤x≤1,0≤y≤1/3,0≤z＜1,0＜m＜1 wherein.This material is with spinel structure LiMn 2-xM xO 4For nuclear, with stratiform Li 1+yMn 1-y-zM ' zO 2Be shell.M, M ' are one or more among Ni, Mg, Cu, Co, Zn, Cr, Fe, the Zr.
Embodiment one
The preparation molecular formula is 0.8LiMn 2O 40.2Li 1.2Mn 0.6Ni 0.2O 2The nucleocapsid structure active material of cathode, its synthetic method is as follows: the 3.2mol manganese sulfate is mixed with 1600ml soluble salt solution I, 0.24mol manganese sulfate, 0.08mol nickelous sulfate are mixed with 160ml soluble salt mixed solution I I, 7.04mol NaOH and 165ml ammoniacal liquor are mixed with 1760ml mixed solution I II.Above-mentioned soluble salt solution I is joined in the reactor of 5L with the identical speed of 3.0ml/min with mixed solution I II, and control reaction temperature is 50 ℃, and the pH value is 10.0, and constantly stirs up to reaction and finish, and reaction was stirred 0.5 hour after finishing again.Continuation joins mixed solution I I in the reactor of above-mentioned 5L with the identical speed of 3.0ml/min with mixed solution I II, and control reaction temperature is 50 ℃, and the pH value is 10.0, constantly stirs up to reaction and finishes, and reaction was stirred 0.5 hour after finishing again.The precipitate and separate, filtration, the drying that obtain are obtained presoma.Above-mentioned presoma and 1.04mol lithium carbonate are put into planetary ball mill mix, rotating speed is 200r/min, and the time is 4h, obtains the precursor mixture.Precursor mixture as in the box type furnace, is naturally cooled to room temperature behind programming rate to the 800 ℃ insulation 12h with 5 ℃/min.Obtain 0.8LiMn through pulverizing, sieving 2O 40.2Li 1.2Mn 0.6Ni 0.2O 2Composite material of core-shell structure.
The composite cathode active material that embodiment one is obtained carries out the SEM detection, and the result as shown in Figure 1.This material is assembled into button cell its chemical property is tested, the charging/discharging voltage scope is 3.0-4.3V, and as shown in Figure 2, discharge capacity is 132.6mAh/g first.
The negative electrode 2 for preparing the rechargeable pond through the following steps.At first, the dry above-mentioned composite cathode active material that synthesize, utilize NMP as solvent with the composite cathode active material, mix as the acetylene black of conductive agent with as the Kynoar of binding agent, so that formation paste cathode mix.The ratio of active material of cathode, acetylene black and Kynoar is 85: 10: 5.Subsequently cathode mix is coated on the aluminum foil current collector, 120 degree are dry 1 hour in vacuum drying oven, obtain negative electrode 2.
Use disk shape lithium sheet metal as anode 4, use the perforated membrane of making by polypropylene, use and wherein dissolved lithium salts LiPF as barrier film 5 6The volume ratio of (concentration is 1mol/L), ethylene carbonate and methyl ethyl carbonate and dimethyl carbonate be that 1: 1: 1 mixed solvent is as electrolyte solution 6.Cell diameter is 20mm, height 3.2mm.
Battery carries out charge-discharge in the following manner.At first, adopt the constant current mode to charge, reach 4.3V up to cell voltage under the constant current mode, adopt the constant voltage mode to charge subsequently, electric current becomes 0.05mA/cm under the constant voltage of 4.3V 2Or it is lower; Next under constant current, discharge, reach 3.0V up to cell voltage.Battery carries out charge and discharge cycles in room temperature (25 ℃) subsequently.
Embodiment two
The preparation molecular formula is 0.8LiMn 1.5Ni 0.5O 40.2Li 1.2Mn 0.6Ni 0.1Co 0.1O 2The nucleocapsid structure active material of cathode, its synthetic method is as follows: 2.4mol manganese sulfate, 0.8mol nickelous sulfate are mixed with 1600ml soluble salt solution I, 0.24mol manganese sulfate, 0.04mol nickelous sulfate, 0.04mol cobaltous sulfate are mixed with 160ml soluble salt mixed solution I I, 7.04mol NaOH and 165ml ammoniacal liquor are mixed with 1760ml mixed solution I II.Above-mentioned soluble salt solution I is joined in the reactor of 5L with the identical speed of 3.0ml/min with mixed solution I II, and control reaction temperature is 50 ℃, and the ph value is 10.0, and constantly stirs up to reaction and finish, and reaction was stirred 0.5 hour after finishing again.Continuation joins mixed solution I I in the reactor of above-mentioned 5L with the identical speed of 3.0ml/min with mixed solution I II, and control reaction temperature is 50 ℃, and the pH value is 10.0, constantly stirs up to reaction and finishes, and reaction was stirred 0.5 hour after finishing again.The precipitate and separate, filtration, the drying that obtain are obtained presoma.Above-mentioned presoma and 1.04mol lithium carbonate are put into planetary ball mill mix, rotating speed is 200r/min, and the time is 4h, obtains the precursor mixture.Precursor mixture as in the box type furnace, is naturally cooled to room temperature behind programming rate to the 800 ℃ insulation 12h with 5 ℃/min.Obtain 0.8LiMn through pulverizing, sieving 1.5Ni 0.5O 40.2Li 1.2Mn 0.6Ni 0.1Co 0.1O 2Composite material of core-shell structure.
The nucleocapsid structure active material of cathode that embodiment two is obtained carries out the SEM detection, and the result as shown in Figure 3.Adopt embodiment 1 same method that this material is assembled into the buckle type lithium-ion secondary cell its chemical property is tested, this moment, the charging/discharging voltage scope changed to 3.0～5.0V, and as shown in Figure 4,70 to take turns capability retention be more than 99%.

Claims (10)

1. nucleocapsid structure active material of cathode, it is characterized in that: the general formula of described nucleocapsid structure active material of cathode is: mLiMn 2-xM xO 4(1-m) Li 1+yMn 1-y-zM ' zO 2, 0≤x≤1,0≤y≤1/3,0≤z＜1,0＜m＜1 wherein, this material is with spinel structure LiMn 2-xM xO 4For nuclear, with stratiform Li 1+yMn 1-y-zM ' zO 2Be shell, M and M ' are one or more among Ni, Mg, Cu, Co, Zn, Cr, Fe, the Zr.
2. nucleocapsid structure active material of cathode according to claim 1 is characterized in that: stratiform Li 1+yMn 1-y-zM ' zO 2Be following crystal structure: LiMnO 2, LiNi 0.5Mn 0.5O 2, Li (Li 1/3Mn 2/3) O 2Perhaps stratiform Li 1+yMn 1-y-zM ' zO 2In M ' be Ni or for Ni and Co.
3. the preparation method of the described nucleocapsid structure active material of cathode of claim 1 is characterized in that described method comprises the steps:
1) mol ratio of the soluble-salt of soluble manganese salt and M being pressed Mn:M is (2-x): x, and wherein the ratio of 0≤x≤1 is mixed with the soluble salt mixed solution I that concentration of metal ions is 0.5-3.0mol/L;
2) mol ratio of the soluble-salt of soluble manganese salt and M ' being pressed Mn:M ' is (1-y-z): z, and wherein the ratio of 0≤y≤1/3,0≤z＜1 is mixed with the soluble salt mixed solution II that concentration of metal ions is 0.5-3.0mol/L;
3) obtain solution III, solution III are alkaline aqueous solution;
4) above-mentioned soluble salt mixed solution I and solution III are evenly joined in the reactor simultaneously continuously react, the control reaction pH value is 9 ~ 11, reaction temperature is 40 ~ 60 ℃, stir in the time of reaction, the reinforced back of finishing continues to stir 0.5 ~ 5 hour, obtain intermediate material, continue to add soluble salt mixed solution II and solution III, the control reaction pH value is 9 ~ 11, reaction temperature is 40 ~ 60 ℃, stirs in the time of reaction, and the reinforced back of finishing continues to stir 0.5 ~ 5 hour, obtain mixed material, wherein control the ratio of nucleocapsid by the consumption of control solution I and solution II;
5) the said mixture material is carried out suction filtration, use deionized water wash, drying to obtain sphere or the spherical presoma of class then;
6) above-mentioned presoma and lithium salts is even by the molecular formula mixed, obtain mixture;
7) with the mixture of step 6) under 400 ~ 600 ℃ of temperature constant temperature 0.5-10 hour, ground the cooling back, calcining at constant temperature 5 ~ 20 hours under 800 ~ 1000 ℃ of temperature again, and cooling, pulverizing, screening, classification obtain final products.
4. method according to claim 3 is characterized in that: described lithium salts is at least a in lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, the lithium fluoride.
5. method according to claim 3 is characterized in that: the soluble-salt of M is one or more in the chloride, fluoride, iodide, sulfate, nitrate, acetate, oxalates of M; The soluble-salt of M ' is one or more in the chloride, fluoride, iodide, sulfate, nitrate, acetate, oxalates of M '.
6. method according to claim 3 is characterized in that: the mixed solution that described alkaline aqueous solution selects for use sodium hydroxide solution or NaOH and ammoniacal liquor to form.
7. method according to claim 6 is characterized in that: the concentration of sodium hydroxide solution is 1.0-4.0mol/L, and ammoniacal liquor and sodium hydroxide solution volume ratio are 1:(5 ~ 15 in the mixed solution that NaOH and ammoniacal liquor form).
8. method according to claim 3 is characterized in that: in the step 6), can directly mix obtaining mixture, perhaps mix in the mixed solution of deionized water, absolute ethyl alcohol or deionized water and absolute ethyl alcohol, obtain mixture after the drying.
9. the negative electrode of a lithium rechargeable battery is characterized in that: comprise the described active material of cathode of any one claim of claim 1 to 8.
10. lithium rechargeable battery, it comprises negative electrode, anode and electrolyte, it is characterized in that: described negative electrode is the described negative electrode of claim 9.
CN2011101505264A 2011-06-07 2011-06-07 Cathode active material with core shell structure, preparation method and secondary battery using material Pending CN102244256A (en)

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CN104157831A (en) * 2014-08-19 2014-11-19 哈尔滨工业大学 Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof
CN104505506A (en) * 2015-01-20 2015-04-08 天津理工大学 High-capacity heterogeneous core-shell structure lithium ion battery positive electrode material and preparation method thereof
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CN107086298A (en) * 2017-04-25 2017-08-22 中南大学 By lithium-rich manganese-based nucleocapsid isomery lithium ion battery composite cathode material constituted with lithium manganate having spinel structure of stratiform and preparation method thereof
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CN109088067A (en) * 2018-09-29 2018-12-25 广东邦普循环科技有限公司 A kind of preparation method of low cobalt doped spinel-layer structure nickel ion doped two-phase composite positive pole
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CN112952056A (en) * 2021-01-27 2021-06-11 中国科学院宁波材料技术与工程研究所 Lithium-rich manganese-based composite cathode material and preparation method and application thereof

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