CN101404329A - Phosphate and lithium titanate composite anode material for lithium ion battery and method for producing the same - Google Patents

Phosphate and lithium titanate composite anode material for lithium ion battery and method for producing the same Download PDF

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CN101404329A
CN101404329A CNA2008100377125A CN200810037712A CN101404329A CN 101404329 A CN101404329 A CN 101404329A CN A2008100377125 A CNA2008100377125 A CN A2008100377125A CN 200810037712 A CN200810037712 A CN 200810037712A CN 101404329 A CN101404329 A CN 101404329A
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lithium
phosphate
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limpo
ion battery
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黄富强
龚思源
刘红仙
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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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a compound positive material of lithium ion battery phosphate and lithium titanate as well as a preparation method thereof; the material containing metal, lithium and phosphorous source or/and superfine LiMPO4 or/and superfine Li4-yTi5O12-sigma react to synthesize the compound material of LiMPO4 and Li4-yTi5O12-sigma having chemical bond and strong physical bond at the temperature under inert gas or reducing atmosphere; the compound positive material with excellent electrochemistry performance is obtained by adding lubricant ball mill. The compound positive material prepared by the method has cheap materials, low cost, unique technique, excellent electrochemistry performance of the production material and easy realization on industrialization.

Description

A kind of lithium ion battery phosphate and titanate composite anode material for lithium and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery phosphate and titanate composite anode material for lithium and preparation method thereof, particularly composite material is by LiMPO 4And Li 4-yTi 5O 12-δForm, by regulating the composite microstructure that preparation technology's controlledly synthesis goes out to have chemical bond or strong physical bond.
Background technology
Lithium ion battery becomes more and more important in the activity of human society as energy storage device, LiFePO 4A kind of anode material for lithium-ion batteries that is considered to have most application prospect with low-cost and fail safe.The research of LiFePO4 at present mainly concentrates on following several aspect: (1) reduces the particle diameter of synthetic material, shorten the evolving path of lithium ion in material, can improve the diffusion rate of lithium ion in material, but can reduce the tap density of material, cause the battery volume energy density to descend; (2) add conductive agent, can improve the electronic conductivity of material, and mostly be adopted as the carbon coating technology, but material with carbon element complex forms and electric conductivity are inconsistent, also can reduce the tap density of material; (3) element doping introduce hetero-atom in order to improve conductivity of electrolyte materials in material lattice, but feasibility and working mechanism is unclear at present, also can reduce theoretical capacity along with doping increases.Method preparing phosphate iron lithium mainly contains high-temperature solid phase reaction method (US6528033, US2004/0151649, CN200410017382.5), liquid phase co-electrodeposition method (WO02/083555A2), sol-gel process (CN1410349A) etc.Because LiFePO4 is a pore passage structure, its electronics and ionic conduction resistance under the long diffusion path of process is bigger, is not used in the high rate capability of electrokinetic cell fast charging and discharging.
The positive electrode that lithium battery is used need be electronics and lithium ion mixed conductor, and the electronic conductivity of LiFePO4 is lower, and therefore need and conductive agent are compound to improve electron transport ability in the electrochemical process.General used method is for adding conductive carbon powder or carbon containing conductive agent presoma ([J] J.F.Ni Progress in Chemistry 16 (4) 554-560 2004, [J] Y.Q.Hu et al Journal of the Electrochemical Society 151 (8) A1279-A1285 2004, [J] S.T.Myung et al Electrochimica Acata 49 (24) 4213-4222 2004, [J] J.Shim et al Journal ofPower Sources 119 955-958 2003, A.S.Andersson et al Journal of Power Sources 97-8:503-507 2001, US6528033, US2004/0151649, CN1410349A).The compound electron conduction ability that can improve material greatly of LiFePO4/carbon.
The ionic conducting property of LiFePO4 is also lower, method commonly used is a nanometer, shorten the evolving path of lithium ion in material, can reduce lithium ion all-in resistance in material, but the tap density of nano-grade lithium iron phosphate is very low, cause the battery volume energy density to descend, also can reduce the electrochemistry and the chemical stability of material.The positive electrode that lithium-ion-power cell is used must have high stored energy capacitance, high-tap density, high power charging-discharging.Except LiFePO 4, LiMPO 4(M is a kind of or combination among Fe, Ti, Cr, Mn, Fe, Co, the Ni) also has excellent chemical property.Have or similar Li with spinel structure 4-yTi 5O 12-δExistence is good lithium ion and electronic conductive material, its charge and discharge platform lower (1.56V vs.Li); Take off in the embedding of lithium ion that structure and volume change hardly in the process.Li 4Ti 5O 12Can be used as high magnification, safe negative material.For LiMPO 4The comprehensive electrochemical that improves is designed composite positive pole (1-x) LiMPO 4-xLi 4-yTi 5O 12-δ, contain high dispersive, that structure is compound, substitute the carbonaceous conductive network, lithium ion battery is with the NEW TYPE OF COMPOSITE positive electrode of lithium phosphate and lithium titanate, further improves li-contained phosphate positive electrode conductivity and tap density.
Summary of the invention
The present invention discloses a kind of lithium ion battery with phosphate and titanate composite anode material for lithium and preparation method thereof, innovates design and preparation that part is composite positive pole.Composite positive pole (1-x) LiMPO that serves as reasons 4-xLi 4-yTi 5O 12-δPhosphate is formed, and micro-structural has the interface or the transition zone (Fig. 1) of chemical bond or strong physical bond between heterostructure, have good ion and electronic conductivity.The present invention (1-x) LiMPO 4-xLi 4-yTi 5O 12-δIn the composite positive pole, LiMPO 4In M be one or more elements among Fe, Mn, Co, Ni, Cu, Ti, the Cr, x and y meet 0＜x≤0.5 and 0≤y≤4, wherein the figure of merit scope of x is 0.05-0.3.
A kind of lithium ion battery is with the preparation method of phosphate and titanate composite anode material for lithium, by (1-x) LiMPO 4-xLi 4-yTi 5O 12-δStoichiometric proportion is in the lithium source, M source, titanium source, phosphorus source, LiMPO 4, Li 4-yTi 5O 12-δThe interior combination raw materials of selecting; evenly mix the back with nitrogen or argon gas or hydrogen nitrogen or hydrogen argon mixing do protection atmosphere, in 3-10 hour, be warming up to 500-850 ℃, insulation reaction 1-10 hour; be cooled to room temperature then and get the compound phase of positive electrode, add lubricant and ball milling refinement and obtain (1-x) LiMPO 4-xLi 4-yTi 5O 12-δComposite positive pole, the addition of lubricant are the 0.25%-10% of the compound phase weight of positive electrode.
Can select material as one of following four kinds of methods:
Implementation method one: the raw material that will contain lithium, M, titanium and phosphate radical is (by (1-x) LiMPO 4-xLi 4-yTi 5O 12-δStoichiometric proportion) evenly mixes;
Implementation method two: with ultra-fine (1-x) LiMPO 4With x Li 4-yTi 5O 12-δRaw material evenly mix;
Implementation method three: with ultra-fine (1-x) LiMPO 4(press xLi with the raw material that will contain lithium, titanium and phosphate radical 4-yTi 5O 12-δStoichiometric proportion) evenly mixes;
Implementation method four: with ultra-fine xLi 4-yTi 5O 12-δ(press (1-x) LiMPO with the raw material that will contain lithium, M and phosphate radical 4Stoichiometric proportion) evenly mixes.
The lithium source that the present invention adopts is a kind of or combination of lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium dihydrogen phosphate.
The phosphorus source that the present invention adopts is a kind of or combination of phosphorus pentoxide, phosphoric acid, phosphoric acid ammonia salt.
M that the present invention adopts and titanium source can be a kind of or combination of metal oxide, metal sulfate, metal phosphate, metal nitrate, metal chloride, metal citrate respectively.
The LiMPO that the present invention adopts 4And Li 4-yTi 5O 12-δIt can be commercially available or homemade superfine powder.
The lubricant that the present invention adds is graphite or molybdenum bisuphide or ethanol, adds fully ball milling refinement of back, looks the actual conditions ball milling 0.5-48 hour.
It is composite phosphate and lithium titanate material and preparation method that the present invention prepares the distinguishing feature of composite positive pole and preparation method thereof: (1) Li 4-yTi 5O 12-δBe good ion cathode material lithium, electronics and ionic conductivity are adjustable flexibly according to Li content and oxygen room; (2) Li 4-yTi 5O 12-δAnd LiMPO 4Form interfacial structure easily, guaranteed conduction charge carrier diffusion, can improve the electrochemical properties of composite material greatly with chemical bond or strong physical bond; (2) with the raw material in containing metal, lithium and phosphorus source or/and ultra-fine LiMPO 4Or/and ultra-fine Li 4-yTi 5O 12-δPyroreaction synthesizes by the LiMPO with chemical bond or strong physical bond under inertia or reducing atmosphere 4And Li 4-yTi 5O 12-δComposite material, add lubricant and ball milling refinement then, obtain the composite positive pole of chemical property excellence.The raw material that the present invention adopts can be cheap chemical products, and synthesis technique is simple, and product is highly suitable for battery and makes, and is easy to large-scale production.
The present invention prepares that lithium ion battery closes phosphate and titanate composite anode material for lithium comprises an amount of Li than simple LiFePO4 innovative point 4-yTi 5O 12-δCan increase lithium ion or electronic conductivity, also can mixing more, multivalent transition metal increases chemical property; This composite material does not need the conductive carbon network, can improve tap density; The Li of high conductivity 4-yTi 5O 12-δThe compound LiMPO that do not need 4The nanometer of particle can improve tap density greatly; Composite positive pole has growth conductive micro structures passage more completely.
Description of drawings
Fig. 1 LiMPO 4-Li 4-yTi 5O 12-δComposite microstructure (being not limited only to given example).
Fig. 2 presses the efficiency curve of the prepared composite positive pole of embodiment 1.
Embodiment
Comparative Examples
A kind of preparation method of lithium ion battery anode material lithium iron phosphate; lithium dihydrogen phosphate, ferrous oxalate are evenly mixed; the mol ratio of controlling phosphorus, iron and lithium in the raw material is 1.0: 1.0: 1.0; make protection atmosphere with argon gas and in 3 hours, be warming up to 350 ℃ and insulation reaction 6 hours; be cooled to room-temperature ball-milling; make protection atmosphere with argon gas and in 5 hours, be warming up to 700 ℃ and insulation reaction 10 hours, obtain lithium iron phosphate positive material.
Active material iron phosphate powder, conductive agent acetylene black and binding agent Kynoar mixed to be applied to by mass ratio at 8: 1: 1 make positive plate on the aluminium foil.In the argon gas atmosphere dry glove box, be to electrode with metal lithium sheet, the UB3025 film is a barrier film, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF 6Be electrolyte, be assembled into the button cell test performance.
Under 20 ± 2 ℃, battery is carried out the constant current charge-discharge test in 2.5V～4.2V voltage range.1C rate charge-discharge specific capacity is 108mAhg -1, through more than 100 cycle battery capacity attenuations to 90%.
Embodiment 1
A kind of lithium ion battery composite lithium iron phosphate 95%LiFePO 4-5%Li 4Ti 5O 12The preparation method of positive electrode evenly mixes ferrous oxide, lithia, phosphorus pentoxide, and it is definite that the mol ratio of phosphorus, iron and lithium is pressed chemical formula, with 5%H 2Nitrogen in 5 hours, be warming up to 650 ℃, insulation reaction 8 hours is cooled to room temperature then, obtains composite material;
Add lubricant graphite in anode composite material, the addition of lubricant is 5% of a composite material weight, and fully after the ball milling refinement, discharging is anode composite material.0.2C/0.2C rate capability is greater than 155mAhg -1, 1C/1C rate charge-discharge specific capacity is 142mAhg -1, unattenuated through more than 500 cycle battery capacity, efficient is near 100 ± 5% (Fig. 2, regular fluctuation among the figure is because due to daytime and the nocturnal temperature environment).
Embodiment 2
A kind of lithium ion battery composite lithium iron phosphate 95%LiFePO 4-5%Li 3Ti 5O 12The preparation method of positive electrode evenly mixes iron hydroxide, lithium carbonate, titanium dioxide, ammonium di-hydrogen phosphate, presses the chemical formula mol ratio and determines, with 5%H 2Nitrogen in 3 hours, be warming up to 500 ℃, insulation reaction 10 hours is cooled to room temperature then, obtains composite material;
Add lubricant graphite in anode composite material, the addition of lubricant is 3% of a composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 138mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 3
A kind of lithium ion battery composite lithium iron phosphate 90%LiFePO 4-10%Li 2Ti 5O 12The preparation method of positive electrode evenly mixes iron hydroxide, lithium carbonate, manganese dioxide, titanium dioxide, ammonium di-hydrogen phosphate, presses the chemical formula mol ratio and determines, with 5%H 2Argon gas in 10 hours, be warming up to 850 ℃, insulation reaction 4 hours is cooled to room temperature then, obtains composite material
Add lubricant molybdenum bisuphide in anode composite material, the addition of lubricant is 1% of an anode composite material weight, and fully behind the ball milling, discharging is the phosphate composite positive pole.1C rate charge-discharge specific capacity is 142mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 4
A kind of lithium ion battery composite lithium iron phosphate 80LiFePO 4-20%Li 4Ti 5O 12The preparation method of positive electrode evenly mixes iron hydroxide, lithium carbonate, titanium dioxide, ammonium di-hydrogen phosphate, presses the chemical formula mol ratio and determines, with 5%H 2Nitrogen in 6 hours, be warming up to 700 ℃, insulation reaction 4 hours is cooled to room temperature then, obtains compound phase;
Add lubricant graphite in anode composite material, the addition of lubricant is 2% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 120mAhg -1, unattenuated through more than 100 cycle battery capacity; 5C rate charge-discharge specific capacity is 110mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 5
A kind of lithium ion battery composite lithium iron phosphate 80%LiFe 0.9Mn 0.1PO 4-20%Li 4Ti 5O 12The preparation method of positive electrode evenly mixes iron hydroxide, lithium carbonate, manganese dioxide, titanium dioxide, ammonium di-hydrogen phosphate, presses the chemical formula mol ratio and determines, in 8 hours, to be warming up to 780 ℃ in the argon gas, insulation reaction 6 hours is cooled to room temperature then, obtains composite material;
Add lubricant molybdenum bisuphide in anode composite material, the addition of lubricant is 2% of an anode composite material weight, and fully behind the ball milling, discharging is the phosphate composite positive pole.1C rate charge-discharge specific capacity is 145mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 6
A kind of lithium ion battery composite lithium iron phosphate 70%LiFePO 4-30%Li 4Ti 5O 12The preparation method of positive electrode is with nano level superfine LiFePO 4With nano level superfine Li 4Ti 5O 12Evenly mix, to be warming up to 700 ℃ in the nitrogen in 3 hours, insulation reaction 1 hour is cooled to room temperature then, obtains composite material;
Add lubricant graphite compound in mutually, the addition of lubricant is 2% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 135mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 7
A kind of lithium ion battery composite lithium iron phosphate 95%LiFePO 4-5%Li 3Ti 5O 11.5The preparation method of (δ=0.5) positive electrode is with nano level superfine LiFePO 4With nano level superfine Li 3Ti 5O 11.5Evenly mix, to be warming up to 700 ℃ in the nitrogen in 3 hours, insulation reaction 1 hour is cooled to room temperature then, obtains composite material;
Add lubricant graphite compound in mutually, the addition of lubricant is 2% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 142mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 8
A kind of lithium ion battery composite lithium iron phosphate 95%LiFePO 4-5%Ti 5O 12(y=4) preparation method of positive electrode is with nano level superfine LiFePO 4With nano level superfine Ti 5O 12Evenly mix, to be warming up to 700 ℃ in the nitrogen in 3 hours, insulation reaction 1 hour is cooled to room temperature then, obtains composite material;
Add lubricant graphite compound in mutually, the addition of lubricant is 2% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 142mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 9
A kind of lithium ion battery composite lithium iron phosphate 50%LiFePO 4-50%Li 4Ti 5O 12The preparation method of positive electrode is with nano level superfine LiFePO 4Evenly mix with ferrous oxalate, lithium carbonate, titanium dioxide, to be warming up to 780 ℃ in the nitrogen in 5 hours, insulation reaction 2 hours is cooled to room temperature then, obtains the compound phase of phosphate;
Add lubricant graphite compound in mutually, the addition of lubricant is 0.25% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 131mAhg -1, unattenuated through more than 100 cycle battery capacity.
Embodiment 10
A kind of lithium ion battery composite lithium iron phosphate 60%LiFePO 4-40%Li 3.5Ti 5O 12The preparation method of positive electrode is with nano level superfine 5%Li 5Fe 2(PO 4) 3Evenly mix with ferrous oxalate, lithium carbonate, titanium dioxide, ammonium di-hydrogen phosphate, with 5%H 2Nitrogen in 6 hours, be warming up to 750 ℃, insulation reaction 1 hour is cooled to room temperature then, obtains compound phase 95%LiFePO 4-5%Li 3.5Ti 5O 12-δ
Add liquid phase lubricant ethanol compound in mutually, the addition of lubricant is 10% of an anode composite material weight, and fully behind the ball milling, discharging is anode composite material.1C rate charge-discharge specific capacity is 137mAhg -1, unattenuated through more than 100 cycle battery capacity.
Annotate: add lubricant and carry out abundant ball milling, looking the actual conditions ball milling time is 0.5-48 hour.

Claims (10)

1. a lithium ion battery is characterized in that the LiMPO by (1-x) with phosphate and titanate composite anode material for lithium 4-xLi 4-yTi 5O 12-δForm, micro-structural has the interface or the transition zone of chemical bond or strong physical bond between heterostructure;
Wherein: 0＜x≤0.5,0≤y≤4;
LiMPO 4In M be one or more elements among Fe, Mn, Co, Ni, Cu, Ti, the Cr.
2. lithium ion battery according to claim 1 phosphate and titanate composite anode material for lithium, the value that it is characterized in that x is 0.05-0.3.
3. lithium ion battery according to claim 1 and 2 is characterized in that with phosphate and titanate composite anode material for lithium lithium titanate is the Li with complete or imperfect crystal type 4-yTi 5O 12-δ
4. lithium ion battery is with the preparation method of phosphate and titanate composite anode material for lithium, it is characterized in that by claim 1,2, one of 3 described (1-x) LiMPO 4-x Li 4-yTi 5O 12-δStoichiometric proportion is in the lithium source, M source, titanium source, phosphorus source, LiMPO 4, Li 4-yTi 5O 12-δThe interior combination raw materials of selecting; evenly mix the back with nitrogen or argon gas or hydrogen argon or hydrogen nitrogen mixing do protection atmosphere, in 3-10 hour, be warming up to 500-850 ℃, insulation reaction 1-10 hour; be cooled to room temperature then and get the compound phase of positive electrode, add the refinement of lubricant ball milling and obtain (1-x) LiMPO 4-x Li 4-yTi 5O 12-δComposite positive pole, the addition of lubricant are the 0.25%-10% of the compound phase weight of positive electrode.
5. preparation method according to claim 4 is characterized in that the phosphorus source is a kind of or combination of phosphorus pentoxide, phosphoric acid, phosphoric acid ammonia salt.
6. preparation method according to claim 4 is characterized in that the lithium source is a kind of or combination of lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium dihydrogen phosphate.
7. preparation method according to claim 4 is characterized in that M and titanium source are respectively a kind of or combination of metal oxide, metal sulfate, metal phosphate, metal nitrate, metal chloride, metal citrate.
8. preparation method according to claim 4 is characterized in that LiMPO 4And Li 4-yTi 5O 12-δIt is commercially available or homemade superfine powder.
9. preparation method according to claim 4 is characterized in that lubricant is graphite or molybdenum bisuphide or ethanol.
10. preparation method according to claim 4 is characterized in that adding behind the lubricant ball milling 0.5-48 hour.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102104142A (en) * 2009-12-16 2011-06-22 清华大学 Ion-doped spherical Li4Ti5O12/C lithium ion battery anode material and preparation method thereof
CN102544498A (en) * 2012-03-12 2012-07-04 安徽安凯汽车股份有限公司 Cathode material of lithium ion battery
CN102709530A (en) * 2012-06-13 2012-10-03 上海空间电源研究所 Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof
CN102709523A (en) * 2012-06-13 2012-10-03 湖南丰源业翔晶科新能源股份有限公司 Process for dispersing carbon nanotubes in electroconductive adhesive of lithium ion battery
CN104393234A (en) * 2014-11-21 2015-03-04 海宁美达瑞新材料科技有限公司 Modified lithium ion battery composite positive pole material and preparation method thereof
CN107768633A (en) * 2017-10-17 2018-03-06 深圳市贝特瑞纳米科技有限公司 A kind of fluorophosphate cladding lithium titanate composite material, preparation method and the usage
CN108023083A (en) * 2017-12-04 2018-05-11 惠州亿纬锂能股份有限公司 A kind of method for lifting battery high-temperature storge quality and overcharge safety energy
CN112599749A (en) * 2020-12-18 2021-04-02 安徽工业大学 High-entropy oxide lithium ion battery cathode material with high conductivity and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102104142A (en) * 2009-12-16 2011-06-22 清华大学 Ion-doped spherical Li4Ti5O12/C lithium ion battery anode material and preparation method thereof
CN102544498A (en) * 2012-03-12 2012-07-04 安徽安凯汽车股份有限公司 Cathode material of lithium ion battery
CN102709530A (en) * 2012-06-13 2012-10-03 上海空间电源研究所 Power lithium ion battery with over-charge and over-discharge protection function and preparation method thereof
CN102709523A (en) * 2012-06-13 2012-10-03 湖南丰源业翔晶科新能源股份有限公司 Process for dispersing carbon nanotubes in electroconductive adhesive of lithium ion battery
CN104393234A (en) * 2014-11-21 2015-03-04 海宁美达瑞新材料科技有限公司 Modified lithium ion battery composite positive pole material and preparation method thereof
CN107768633A (en) * 2017-10-17 2018-03-06 深圳市贝特瑞纳米科技有限公司 A kind of fluorophosphate cladding lithium titanate composite material, preparation method and the usage
CN108023083A (en) * 2017-12-04 2018-05-11 惠州亿纬锂能股份有限公司 A kind of method for lifting battery high-temperature storge quality and overcharge safety energy
CN112599749A (en) * 2020-12-18 2021-04-02 安徽工业大学 High-entropy oxide lithium ion battery cathode material with high conductivity and preparation method thereof

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