CN110085828A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN110085828A
CN110085828A CN201910335394.9A CN201910335394A CN110085828A CN 110085828 A CN110085828 A CN 110085828A CN 201910335394 A CN201910335394 A CN 201910335394A CN 110085828 A CN110085828 A CN 110085828A
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lithium
ion batteries
anode material
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zinc
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李箐
陈仙
王谭源
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Huazhong University of Science and Technology
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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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Abstract

The invention belongs to anode material for lithium-ion batteries correlative technology fields, and it discloses a kind of anode material for lithium-ion batteries and preparation method thereof, method includes the following steps: (1) is with ternary precursor NixCoyMn1‑x‑y(OH)2It is that raw material is mixed and roasted to obtain tertiary cathode material LiNi with lithium saltsxCoyMn1‑x‑yO2, 0.5≤x≤0.8,0.1≤y≤0.2；It handles after methanol solution dissolved with cobalt salt and zinc salt to be poured into the methanol solution of methylimidazole to obtain the bimetallic organic framework containing cobalt and zinc；(2) by tertiary cathode material LiNixCoyMn1‑x‑yO2It is calcined after mixing with bimetallic organic framework to obtain anode material for lithium-ion batteries, which is coated with bimetallic oxide.Structure of the invention is stablized, and electric conductivity is preferable, and improves material high rate performance and cycle performance.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries correlative technology fields, more particularly, to a kind of lithium ion battery Positive electrode and preparation method thereof.
Background technique
In recent years, lithium ion battery is widely used in the every aspect of life, from portable electronic device to Electric car and large-scale energy storage system all be unable to do without their presence.Therefore, close to battery higher energy in order to meet people The demand of the requirement of degree, high security and long-life, how to develop new electrode materials and modified original commercialization material becomes The hot spot of research.At present, it is common to use anode material for lithium-ion batteries be cobalt acid lithium, LiFePO4 and ternary material, three First material NCM and NCA because its higher specific discharge capacity and lower cost are considered being expected to replace cobalt acid lithium and LiFePO4, As the widely used power battery anode material of next point.However, high-content of the nickelic ternary material because of its nickel element, and And the ionic radius size of nickel ion and lithium ion is closer to, and is easy to happen during material preparation and electrochemistry circulation This phenomenon of lithium nickel mixing, so that the unstable of material structure is caused, so that material fracture, dusting.In addition, in charge and discharge cycles In the process, it is contacted due to electrolyte with the direct of electrode material, a series of side reaction occurs on contact surface, leads to surface phase transformation Generation, cause the capacity of battery gradually to decline.
In order to alleviate the problem present on, the Normal practice of use is to carry out surface cladding to tertiary cathode material, Cladding aspect, wet chemistry method such as collosol and gel and coprecipitation can usually introduce some impurity and be caused to raw material Particle aggregation and irregular crack, to affect the integrality of cladding；Other methods such as chemical meteorology deposition and original Although sublayer deposition can make clad densification with continuously, often obtained clad is not porous, electric conductivity Poor, this process for making lithium ion be transmitted to internal layer active material from clad is obstructed.Correspondingly, there is development for this field A kind of technical need of the preferable anode material for lithium-ion batteries of electric conductivity and preparation method thereof.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of anode material for lithium-ion batteries and It is preferable to study and devise a kind of electric conductivity based on the work characteristics of existing anode material for lithium-ion batteries for preparation method Anode material for lithium-ion batteries and preparation method thereof.The cladding presoma that the preparation method is selected is containing metallic cobalt and metallic zinc Bimetallic ZIF, ZIF be it is a kind of passed through by transition metal ions and the organic imidazoles rouge of organic ligand be self-assembly of there is week The crystalline porous material of phase property network structure, and by simple and easy mechanical mixture and heat treatment method, it will be unformed double Metal oxide is coated on above tertiary cathode material, which protects anode under the premise of not inhibiting lithium ion transport Material is directly contacted with electrolyte, maintains stable structure, so that the material multiplying power and cycle performance after coating modification obtain Promotion by a relatively large margin, electric conductivity are preferable.
To achieve the above object, according to one aspect of the present invention, a kind of system of anode material for lithium-ion batteries is provided Preparation Method, the preparation method the following steps are included:
(1) with ternary precursor NixCoyMn1-x-y(OH)2It is that raw material is mixed and roasted to obtain ternary just with lithium salts Pole material LiNixCoyMn1-x-yO2, wherein 0.5≤x≤0.8,0.1≤y≤0.2；Meanwhile the first that cobalt salt and zinc salt will be dissolved with Alcoholic solution is handled after pouring into the methanol solution of methylimidazole to obtain the bimetallic organic framework containing cobalt and zinc；
(2) by the tertiary cathode material LiNixCoyMn1-x-yO2After mixing with the bimetallic organic framework It is calcined to obtain modified anode material for lithium-ion batteries, which is coated with bimetallic oxidation Object.
Further, by ternary precursor NixCoyMn1-x-y(OH)2Ball is carried out after mixing with lithium salts according to predetermined molar ratio Mill then roasts under predetermined atmosphere to obtain tertiary cathode material LiNixCoyMn1-x-yO2。
Further, the predetermined molar ratio is 1:1.5~1:1.
Further, for the Ball-milling Time used when ball milling for 0.5h~2h, rotational speed of ball-mill is 200r/min~400r/min.
Further, for the maturing temperature used when roasting for 700 DEG C~900 DEG C, calcining time is 10h~20h.
Further, the concentration ratio for preparing cobalt salt and zinc salt is (1~5): 1 methanol solution, and obtained methanol is molten Liquid pours into the methanol solution for the methylimidazole that concentration is 0.2mol/L~0.6mol/L, and obtained mixed solution is stood 12h ~for 24 hours after be successively centrifuged, washed and dried after obtain the bimetallic organic frame containing metallic cobalt and metallic zinc.
Further, the volume of the methanol solution of the volume and methylimidazole of the methanol solution dissolved with cobalt salt and zinc salt The ratio between be (0.5~2): 1.
Further, the lithium salts is lithium titanate, a hydronium(ion) lithia, lithium oxalate, lithium acetate, lithium chloride and lithium sulfate One of or it is several；The cobalt salt is one of cobalt nitrate, cobalt chloride, cobalt acetate or several；The zinc salt is nitre One of sour zinc, zinc chloride and zinc acetate are several.
Other side according to the invention provides a kind of anode material for lithium-ion batteries, the lithium ion cell positive Material is prepared using the preparation method of anode material for lithium-ion batteries as described above；The lithium ion cell positive material Material includes tertiary cathode material and clad, and the clad is coated on the tertiary cathode material；The clad includes Equally distributed zinc oxide and cobalt oxide.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, lithium provided by the invention Ion battery positive electrode and preparation method thereof mainly has the advantages that
1. the present invention select ZIF as cladding presoma, the presoma have high porosity, low-density, bigger serface, The advantages that duct is regular fully can be mixed uniformly with tertiary cathode material, be obtained uniformly after Post isothermal treatment on surface Unformed shape oxide cladding layers.
2. the preparation method is by simple and easy mechanical mixture and heat treatment method, by unformed bimetallic oxide It is coated on above tertiary cathode material, which protects positive electrode and electrolysis under the premise of not inhibiting lithium ion transport Liquid directly contacts, and maintains stable structure, improves electric conductivity.
3. the present invention is prepared for the bimetallic ZIF containing zinc and cobalt, zinc oxide and cobalt oxide are all the cladding being excellent in Layer, the two is combined, ion adulterates each other, and obtained oxide cladding layers electric conductivity is more preferable, and the high rate performance of battery is more excellent It is different.
4. provided by the invention, preparation method is simple, the reproducible, anode material for lithium-ion batteries that is prepared There are higher reversible specific capacity and better cyclical stability.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method of anode material for lithium-ion batteries provided by the invention；
Fig. 2 is the scanning for the bimetallic ZIF being prepared using the preparation method of the anode material for lithium-ion batteries in Fig. 1 Electron microscope；
Fig. 3 is the scanning electron microscope for the sample being prepared using the preparation method of the anode material for lithium-ion batteries in Fig. 1 Figure；
Fig. 4 is the sample for the different component being prepared using the preparation method of the anode material for lithium-ion batteries in Fig. 1 X-ray diffractogram, wherein NCM622/Co-2%, indicate be added the ZIF containing Co, the quality of ZIF67 is the 2% of NCM622； NCM622/Zn-2% indicates ZIF of the addition containing Zn, and the quality of ZIF8 is the 2% of NCM622；NCM622/Co:Zn=1:5- 2%, it indicates that bimetallic ZIF, BMZIF (the Bi-metal Zeolitic Imidazolate containing Co and Zn is added Frameworks:BMZIF quality) is the 2% of NCM622, and wherein the molar ratio of Co and Zn is 5:1；
Fig. 5 is the sample for the different component being prepared using the preparation method of the anode material for lithium-ion batteries in Fig. 1 High rate performance figure；
Fig. 6 is the sample for the different component being prepared using the preparation method of the anode material for lithium-ion batteries in Fig. 1 Cycle performance figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
Fig. 1 and Fig. 2 is please referred to, the preparation method of anode material for lithium-ion batteries provided by the invention mainly includes following step It is rapid:
Step 1, with ternary precursor NixCoyMn1-x-y(OH)2It is that raw material is mixed and roasted to obtain three with lithium salts First positive electrode LiNixCoyMn1-x-yO2。
Specifically, by ternary precursor NixCoyMn1-x-y(OH)2Ball milling is carried out after mixing with lithium salts according to predetermined molar ratio, Then it roasts under predetermined atmosphere to obtain tertiary cathode material LiNixCoyMn1-x-yO2.Wherein, 0.5≤x≤0.8,0.1≤y ≤0.2。
More specifically, by NixCoyMn1-x-y(OH)2It is added in ball mill with lithium salts according to molar ratio 1:1.5~1:1 Ball milling 0.5h~2h is carried out, drum's speed of rotation is 200r/min~400r/min, and obtained product is put into horse after the completion by ball milling 10h~20h is sintered in furnace, at 700 DEG C~900 DEG C not to obtain tertiary cathode material LiNixCoyMn1-x-yO2。
In present embodiment, the lithium salts can be lithium titanate, a hydronium(ion) lithia, lithium oxalate, lithium acetate, lithium chloride And one of lithium sulfate or several.
Step 2 is handled after the methanol solution dissolved with cobalt salt and zinc salt to be poured into the methanol solution of methylimidazole To obtain the bimetallic organic framework containing cobalt and zinc.
Specifically, the concentration ratio for preparing cobalt salt and zinc salt is (1~5): 1 methanol solution, and the methanol solution that will be obtained Pour into concentration be 0.2mol/L~0.6mol/L methylimidazole methanol solution, by obtained mixed solution stand 12h~ The bimetallic ZIF (BMZIF) containing metallic cobalt and metallic zinc is obtained after being successively centrifuged, washed and being dried after for 24 hours, wherein ZIF is zeolite imidazole ester frame structure material.
In present embodiment, the methanol solution of the volume and methylimidazole of the methanol solution dissolved with cobalt salt and zinc salt The ratio between volume is (0.5~2): 1；The cobalt salt is one of cobalt nitrate, cobalt chloride, cobalt acetate or several；The zinc salt For one of zinc nitrate, zinc chloride and zinc acetate or several.Certainly, step 1 and step 2 sequence in no particular order, and two Person can carry out simultaneously.
Step 3, by the tertiary cathode material LiNixCoyMn1-x-yO2It is mixed with the bimetallic organic framework It is calcined after even to obtain modified anode material for lithium-ion batteries, which is coated with bimetallic oxidation Object.
Specifically, the tertiary cathode material LiNi that will be obtainedxCoyMn1-x-yO2With obtained BMZIF according to mass ratio 100: (1~5) is put under scheduled atmosphere sintering 0.5h~2h after being sufficiently mixed, with obtain the lithium of bimetallic oxide cladding from Sub- battery tertiary cathode material.In present embodiment, the calcination temperature used is 500 DEG C~700 DEG C；When mixing by the way of For one of ball milling, grinding and wet mixing.
Fig. 3, Fig. 4, Fig. 5 and Fig. 6 are please referred to, the present invention also provides a kind of anode material for lithium-ion batteries, the lithium ions Cell positive material includes tertiary cathode material and clad, and the clad is coated on the tertiary cathode material.It is described The diameter of tertiary cathode material is 5 μm~10 μm；The clad includes equally distributed zinc oxide and cobalt oxide, and its thickness For 10nm~30nm.
With several specific embodiments, the present invention is further described in detail below.
Embodiment 1
The preparation method for the anode material for lithium-ion batteries that the embodiment of the present invention 1 provides mainly comprises the steps that
S1, by Ni6Co2Mn2(OH)21:1 is added in ball mill in molar ratio with lithium salts, Ball-milling Time 1h, ball mill Revolving speed is 300r/min, and obtained product is put into Muffle furnace after the completion of ball milling and is sintered 10h at 900 DEG C to obtain ternary just Pole material；
The concentration of S2, configuration zinc nitrate and cobalt nitrate is respectively the methanol solution of 0.05mol/L and 0.01mol/L 50ml, and the concentration for pouring into 50ml be 0.2mol/L methylimidazole methanol solution, after obtained mixed liquor is stood for 24 hours, By obtaining the bimetallic ZIF (BMZIF) containing metallic cobalt and zinc after centrifugation, washing, drying.
S3 is put after being sufficiently mixed obtained tertiary cathode material and obtained BMZIF powder 100:1 in mass ratio Enter to be sintered 1h under scheduled atmosphere to get the lithium ion tertiary cathode material coated to bimetallic oxide.
Embodiment 2
The preparation method for the anode material for lithium-ion batteries that the embodiment of the present invention 2 provides mainly comprises the steps that
S1, by Ni6Co2Mn2(OH)21:1.3 is added in ball mill in molar ratio with lithium salts, Ball-milling Time 1h, ball milling Machine revolving speed is 300r/min, and obtained product is put into Muffle furnace after the completion of ball milling and is sintered 15h at 800 DEG C to obtain ternary Positive electrode；
The concentration of S2, configuration zinc nitrate and cobalt nitrate is respectively the methanol solution of 0.04mol/L and 0.04mol/L 25ml, and the concentration for pouring into 50ml be 0.2mol/L methylimidazole methanol solution, after obtained mixed liquor is stood for 24 hours, By obtaining the bimetallic ZIF (BMZIF) containing metallic cobalt and zinc after centrifugation, washing, drying.
S3 is put after being sufficiently mixed obtained tertiary cathode material and obtained BMZIF powder 60:1 in mass ratio Enter to be sintered 1.5h under scheduled atmosphere to get the lithium ion tertiary cathode material coated to bimetallic oxide.In this step, adopt Sintering temperature is 700 DEG C.
Embodiment 3
The preparation method for the anode material for lithium-ion batteries that the embodiment of the present invention 3 provides mainly comprises the steps that
S1, by Ni6Co2Mn2(OH)21:1.5 is added in ball mill in molar ratio with lithium salts, Ball-milling Time 0.5h, ball Mill speed is 400r/min, and obtained product is put into Muffle furnace after the completion of ball milling and is sintered 20h at 700 DEG C to obtain three First positive electrode；
The concentration of S2, configuration zinc nitrate and cobalt nitrate is respectively the methanol solution of 0.04mol/L and 0.04mol/L 50ml, and the concentration of 100ml is poured into as the methanol solution of the methylimidazole of 0.4mol/L, after obtained mixed liquor standing 12h, By obtaining the bimetallic ZIF (BMZIF) containing metallic cobalt and zinc after centrifugation, washing, drying.
S3 is put after being sufficiently mixed obtained tertiary cathode material and obtained BMZIF powder 20:1 in mass ratio Enter to be sintered 0.5h under scheduled atmosphere to get the lithium ion tertiary cathode material coated to bimetallic oxide.In this step, adopt Sintering temperature is 600 DEG C.
Embodiment 4
The preparation method for the anode material for lithium-ion batteries that the embodiment of the present invention 4 provides mainly comprises the steps that
S1, by Ni6Co2Mn2(OH)21:1.1 is added in ball mill in molar ratio with lithium salts, Ball-milling Time 1.5h, ball Mill speed is 300r/min, and obtained product is put into Muffle furnace after the completion of ball milling and is sintered 12h at 850 DEG C to obtain three First positive electrode；
The concentration of S2, configuration zinc nitrate and cobalt nitrate is respectively the methanol solution 100ml of 0.03mol/L and 0.01mol/L, And the concentration for pouring into 50ml be 0.6mol/L methylimidazole methanol solution, after obtained mixed liquor is stood for 24 hours, by from The bimetallic ZIF (BMZIF) containing metallic cobalt and zinc is obtained after the heart, washing, drying.
S3 is put after being sufficiently mixed obtained tertiary cathode material and obtained BMZIF powder 100:2 in mass ratio Enter to be sintered 1.5h under scheduled atmosphere to get the lithium ion tertiary cathode material coated to bimetallic oxide.
Embodiment 5
The preparation method for the anode material for lithium-ion batteries that the embodiment of the present invention 5 provides mainly comprises the steps that
S1, by Ni6Co2Mn2(OH)21:1.1 is added in ball mill in molar ratio with lithium salts, Ball-milling Time 2h, ball milling Machine revolving speed is 200r/min, and obtained product is put into Muffle furnace after the completion of ball milling and is sintered 12h at 850 DEG C to obtain ternary Positive electrode；
The concentration of S2, configuration zinc nitrate and cobalt nitrate is respectively the methanol solution of 0.05mol/L and 0.01mol/L 50ml, and the concentration for pouring into 50ml be 0.5mol/L methylimidazole methanol solution, after obtained mixed liquor is stood for 24 hours, By obtaining the bimetallic ZIF (BMZIF) containing metallic cobalt and zinc after centrifugation, washing, drying.
S3 is put after being sufficiently mixed obtained tertiary cathode material and obtained BMZIF powder 100:2 in mass ratio Enter to be sintered 2h under scheduled atmosphere to get the lithium ion tertiary cathode material coated to bimetallic oxide.In this step, use Sintering temperature be 500 DEG C.
It is mixed to be somebody's turn to do the machinery that preparation method is simple for anode material for lithium-ion batteries provided by the invention and preparation method thereof Conjunction and heat treatment method, unformed bimetallic oxide are coated on above tertiary cathode material, which is not inhibiting It protects positive electrode directly to contact under the premise of lithium ion transport with electrolyte, maintains stable structure, improve electric conductivity Energy.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of anode material for lithium-ion batteries, which is characterized in that the preparation method the following steps are included:
(1) with ternary precursor NixCoyMn1-x-y(OH)2It is that raw material is mixed and roasted to obtain tertiary cathode material with lithium salts Expect LiNixCoyMn1-x-yO2, wherein 0.5≤x≤0.8,0.1≤y≤0.2；Meanwhile it is the methanol dissolved with cobalt salt and zinc salt is molten Liquid is handled after pouring into the methanol solution of methylimidazole to obtain the bimetallic organic framework containing cobalt and zinc；
(2) by the tertiary cathode material LiNixCoyMn1-x-yO2It is carried out after mixing with the bimetallic organic framework To obtain modified anode material for lithium-ion batteries, which is coated with bimetallic oxide for calcining.
2. the preparation method of anode material for lithium-ion batteries as described in claim 1, it is characterised in that: by ternary precursor NixCoyMn1-x-y(OH)2Ball milling is carried out after mixing with lithium salts according to predetermined molar ratio, is then roasted under predetermined atmosphere to obtain Tertiary cathode material LiNixCoyMn1-x-yO2。
3. the preparation method of anode material for lithium-ion batteries as claimed in claim 2, it is characterised in that: the predetermined molar ratio For 1:1.5~1:1.
4. the preparation method of anode material for lithium-ion batteries as claimed in claim 2, it is characterised in that: the ball used when ball milling Time consuming is 0.5h~2h, and rotational speed of ball-mill is 200r/min~400r/min.
5. the preparation method of anode material for lithium-ion batteries as claimed in claim 2, it is characterised in that: the roasting used when roasting Burning temperature is 700 DEG C~900 DEG C, and calcining time is 10h~20h.
6. the preparation method of anode material for lithium-ion batteries as described in claim 1, it is characterised in that: prepare cobalt salt and zinc salt Concentration ratio be (1~5): 1 methanol solution, and it is 0.2mol/L~0.6mol/L that obtained methanol solution, which is poured into concentration, The methanol solution of methylimidazole stands obtained mixed solution after being successively centrifuged, washed and dried after 12h~for 24 hours Obtain the bimetallic organic frame containing metallic cobalt and metallic zinc.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that: be dissolved with cobalt salt and zinc The ratio between volume and the volume of methanol solution of methylimidazole of the methanol solution of salt are (0.5~2): 1.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterised in that: the lithium salts is metatitanic acid One of lithium, a hydronium(ion) lithia, lithium oxalate, lithium acetate, lithium chloride and lithium sulfate are several；The cobalt salt is nitric acid One of cobalt, cobalt chloride, cobalt acetate are several；The zinc salt be one of zinc nitrate, zinc chloride and zinc acetate or It is several.
9. as the described in any item anode material for lithium-ion batteries of claim 1-8 preparation method, it is characterised in that: by this three First positive electrode LiNixCoyMn1-x-yO2With the bimetallic organic framework according to mass ratio 100:(1~5) mixed after It is put into sintering 0.5h~2h under predetermined atmosphere, to obtain the anode material for lithium-ion batteries of bimetallic oxide cladding.
10. a kind of anode material for lithium-ion batteries, it is characterised in that: the anode material for lithium-ion batteries is using claim 1- What the preparation method of 9 described in any item anode material for lithium-ion batteries was prepared；The anode material for lithium-ion batteries includes Tertiary cathode material and clad, the clad are coated on the tertiary cathode material；The clad includes uniformly dividing The zinc oxide and cobalt oxide of cloth.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110707311A (en) * 2019-11-03 2020-01-17 吉林大学 High-nickel ternary material and nano zinc oxide composite cathode material and preparation method thereof
CN111129463A (en) * 2019-12-26 2020-05-08 格林美股份有限公司 Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof
CN111640928A (en) * 2020-06-30 2020-09-08 蜂巢能源科技有限公司 NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery
CN111668465A (en) * 2020-06-05 2020-09-15 国网内蒙古东部电力有限公司电力科学研究院 Modification method of ZIF-8 derivative ZnO in-situ coated lithium nickel cobalt aluminate positive electrode material
CN112820867A (en) * 2021-02-18 2021-05-18 南通国轩新能源科技有限公司 Preparation method of Zn-based MOF electrode material coated ternary cathode material
CN113611856A (en) * 2021-06-08 2021-11-05 贝特瑞（江苏）新材料科技有限公司 Cathode material, preparation method thereof and lithium ion battery
CN114613991A (en) * 2022-03-21 2022-06-10 厦门厦钨新能源材料股份有限公司 Directional synergistic doped lithium cobalt oxide material and preparation method thereof
CN115863612A (en) * 2023-02-21 2023-03-28 四川新能源汽车创新中心有限公司 Positive electrode material and preparation method and application thereof
CN117080417A (en) * 2023-10-16 2023-11-17 宁波容百新能源科技股份有限公司 Ternary positive electrode material, preparation method thereof and lithium ion battery
CN117894971A (en) * 2024-03-18 2024-04-16 中南大学 Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099047A (en) * 2016-08-25 2016-11-09 深圳市贝特瑞纳米科技有限公司 A kind of surface coating method of electrode material and application thereof
CN108807864A (en) * 2017-04-28 2018-11-13 三星电子株式会社 Composite cathode active material, the anode containing composite cathode active material and lithium battery and the method for preparing composite cathode active material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099047A (en) * 2016-08-25 2016-11-09 深圳市贝特瑞纳米科技有限公司 A kind of surface coating method of electrode material and application thereof
CN108807864A (en) * 2017-04-28 2018-11-13 三星电子株式会社 Composite cathode active material, the anode containing composite cathode active material and lithium battery and the method for preparing composite cathode active material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENDONG HAO等: "In situ growth of Co3O4 coating layer derived from MOFs on LiNi0.8Co0.15Al0.05O2 cathode materials", 《IONICS》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110707311B (en) * 2019-11-03 2021-09-21 吉林大学 High-nickel ternary material and nano zinc oxide composite cathode material and preparation method thereof
CN110707311A (en) * 2019-11-03 2020-01-17 吉林大学 High-nickel ternary material and nano zinc oxide composite cathode material and preparation method thereof
CN111129463B (en) * 2019-12-26 2020-11-17 格林美股份有限公司 Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof
CN111129463A (en) * 2019-12-26 2020-05-08 格林美股份有限公司 Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof
CN111668465A (en) * 2020-06-05 2020-09-15 国网内蒙古东部电力有限公司电力科学研究院 Modification method of ZIF-8 derivative ZnO in-situ coated lithium nickel cobalt aluminate positive electrode material
CN111640928A (en) * 2020-06-30 2020-09-08 蜂巢能源科技有限公司 NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery
CN112820867A (en) * 2021-02-18 2021-05-18 南通国轩新能源科技有限公司 Preparation method of Zn-based MOF electrode material coated ternary cathode material
CN113611856A (en) * 2021-06-08 2021-11-05 贝特瑞（江苏）新材料科技有限公司 Cathode material, preparation method thereof and lithium ion battery
CN114613991A (en) * 2022-03-21 2022-06-10 厦门厦钨新能源材料股份有限公司 Directional synergistic doped lithium cobalt oxide material and preparation method thereof
CN115863612A (en) * 2023-02-21 2023-03-28 四川新能源汽车创新中心有限公司 Positive electrode material and preparation method and application thereof
CN117080417A (en) * 2023-10-16 2023-11-17 宁波容百新能源科技股份有限公司 Ternary positive electrode material, preparation method thereof and lithium ion battery
CN117080417B (en) * 2023-10-16 2024-01-26 宁波容百新能源科技股份有限公司 Ternary positive electrode material, preparation method thereof and lithium ion battery
CN117894971A (en) * 2024-03-18 2024-04-16 中南大学 Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof
CN117894971B (en) * 2024-03-18 2024-06-04 中南大学 Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof

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Application publication date: 20190802