CN110336007A - A kind of monocrystalline type battery material and preparation method thereof - Google Patents

A kind of monocrystalline type battery material and preparation method thereof Download PDF

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Publication number
CN110336007A
CN110336007A CN201910609435.9A CN201910609435A CN110336007A CN 110336007 A CN110336007 A CN 110336007A CN 201910609435 A CN201910609435 A CN 201910609435A CN 110336007 A CN110336007 A CN 110336007A
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compound
nickel
cobalt
preparation
monocrystalline type
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刘加兵
其他发明人请求不公开姓名
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Suzhou Lava Lithium Energy Technology Co Ltd
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Suzhou Lava Lithium Energy Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a kind of monocrystalline type battery materials and preparation method thereof, it is mixed by nickel compound containing, cobalt compound, containing manganese compound, excessive lithium source with inorganic fused salt, monocrystalline type nickel-cobalt lithium manganate cathode material is obtained using the calcining manners of multistage alternating temperature, or mix nickel compound containing, cobalt compound, aluminum contained compound, excessive lithium source with inorganic fused salt, monocrystalline type nickel cobalt lithium aluminate cathode material is obtained using the calcining manners of multistage alternating temperature.Through the above way, the present invention is using excessive lithium source, multistage alternating temperature technology, prepare large-sized nickel-cobalt lithium manganate material or nickel cobalt aluminic acid lithium material, excessive lithium source is able to solve product and lacks lithium phenomenon, excessive lithium source can be used as fused salt, enhance dissolubility of the raw material in fused salt, in addition, using multistage alternating temperature technology, the larger-size positive electrode with good chemical property can be prepared.

Description

A kind of monocrystalline type battery material and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of monocrystalline type battery material and its preparation side Method.
Background technique
Lithium ion battery is a kind of rechargeable battery, it relies primarily on lithium ion, and movement carrys out work between a positive electrode and a negative electrode. In charge and discharge process, Li+ insertion and deintercalation back and forth between two electrodes: when charging, Li+ is from positive deintercalation, by electrolysis Matter is embedded in cathode, and cathode is in lithium-rich state；It is then opposite when electric discharge.The main composition material of lithium ion battery include electrolyte, Isolated material, positive and negative pole material etc..Positive electrode occupies larger proportion, and the performance of positive electrode directly affects lithium ion battery Performance, cost also directly determine battery cost height.Existing molten-salt growth method prepares high ni-type nickel-cobalt lithium manganate cathode material Or the method for nickel cobalt lithium aluminate cathode material will lead to the especially high ni-type product of product and occurred seriously using the lithium source of metering ratio The phenomenon that lacking lithium.In addition, general molten-salt growth method is calcined using fixed temperature, calcination temperature cannot be excessively high, otherwise can cause cation Mixing, so as to cause deterioration in material properties.But the relatively low single crystal grain that will cause preparation of calcination temperature is smaller, material compacted density Low, volume energy density is low.In addition, the method (solid phase, fused salt) for currently preparing nickelic ternary material is required using by coprecipitated Containing there are three types of the hydroxide precursors of metal while reaction of forming sediment is prepared.Such presoma price is higher, preparation process Complexity, and production process generates the largely alkaline waste water containing ammonia and heavy metal ion, deals with improperly and will lead to environmental pollution.Cause This, needs to develop the ternary material preparation method independent of coprecipitation reaction precursor.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of monocrystalline type battery materials and preparation method thereof, can prepare The larger-size material with good chemical property.
In order to solve the above technical problems, one technical scheme adopted by the invention is that: a kind of monocrystalline type battery material is provided, The monocrystalline type battery material is nickel-cobalt lithium manganate cathode material or nickel cobalt lithium aluminate cathode material, the nickle cobalt lithium manganate anode The chemical formula of material is LiaNixCoyMnzO2, wherein 1.0≤a≤1.1,0≤x≤1,0≤y≤1,0≤z≤1, and x+y+z= 1, the chemical formula of the nickel cobalt lithium aluminate cathode material is LibNiuCovAlwO2, wherein 1.0≤b≤1.1,0≤u≤1,0≤v ≤ 1,0≤w≤1, and u+v+w=1.
A kind of preparation method of monocrystalline type battery material, including step are provided are as follows: by nickel compound containing, cobalt compound, Monocrystalline type nickel-cobalt lithium manganate cathode material is obtained containing manganese compound, excessive lithium source and inorganic fused salt mixed calcining, or by nickeliferousization It closes object, cobalt compound, aluminum contained compound, excessive lithium source and inorganic fused salt mixed calcining and obtains monocrystalline type nickel cobalt lithium aluminate anode Material, wherein the process of the calcining are as follows: with the heating rate of 10 DEG C/min, be heated to 1000 DEG C, kept for 5 hours, then with 2 DEG C/rate of temperature fall of min is cooled to 900 DEG C, kept for 15 hours, be cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then from It is so cooled to room temperature, obtains head product, head product is calcined again to obtain final product.The process calcined again are as follows: by primiparity Object is 5 hours dry in 80 DEG C, then with the heating rate of 10 DEG C/min, is heated to 750 DEG C, is kept for 10 hours, with the drop of 2 DEG C/min Warm rate is cooled to 200 DEG C, then cooled to room temperature, obtains final product.
In a preferred embodiment of the present invention, the nickel compound containing is oxide NiO, hydroxide Ni (OH)2, nitre Hydrochlorate Ni (NO3)2, oxalates NiC2O4One of or a variety of mixtures.
In a preferred embodiment of the present invention, the cobalt compound is oxide CoO, oxide Co2O3, hydroxide Object Co (OH)2, nitrate Co (NO3)2, oxalates CoC2O4One of or a variety of mixtures.
In a preferred embodiment of the present invention, the manganese compound that contains is oxide M nO, oxide M nO2, hydroxide Object Mn (OH)2, nitrate Mn (NO3)2, oxalates MnC2O4One of or a variety of mixtures.
In a preferred embodiment of the present invention, the aluminum contained compound is oxide Al2O3, hydroxide Al (OH)3、 Nitrate Al (NO3)3, oxalates Al2 (C2O4)3One of or a variety of mixtures.
In a preferred embodiment of the present invention, the lithium source is LiOH, LiNO3、Li2CO3One of or a variety of mixing Object.
In a preferred embodiment of the present invention, the lithium source and the nickel compound containing, the cobalt compound, described Molar ratio >=1.2 of the summation containing manganese compound；The lithium source and the nickel compound containing, described contain aluminium at the cobalt compound Molar ratio >=1.2 of compound summation.
In a preferred embodiment of the present invention, the inorganic fused salt is Li2SO4、Na2SO4、K2SO4、Rb2SO4、 Cs2SO4、LiF、LiCl、NaCl、KCl、RbCl、CsCl、BaCl2、CaCl、Li2CO3、Na2CO3、K2CO3、LiNO3、NaNO3、 One of LiOH, NaOH, KOH or a variety of mixtures, mixed proportion can be any mole of metering ratio.
In a preferred embodiment of the present invention, described to be mixed into dry grinding, wet grinding, dry ball milling or wet process ball Mill.
The beneficial effects of the present invention are: monocrystalline type battery material and preparation method thereof of the invention, using excessive lithium source, more Duan Bianwen technology prepares large-sized nickel-cobalt lithium manganate material or nickel cobalt aluminic acid lithium material, and excessive lithium source can in the present invention It solves product and lacks lithium phenomenon, excessive lithium source can be used as fused salt, enhance dissolubility of the raw material in fused salt, in addition, being directed to fused salt The small problem of the nickelic crystalline product particle of method preparation, uses multistage alternating temperature technology, can prepare larger-size with good The positive electrode of good chemical property.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing, in which:
Fig. 1 is the SEM figure of embodiment product in battery material of the present invention and preparation method thereof；
Fig. 2 is that the electrochemistry of embodiment nine, ten and comparative example four circulation is surveyed in battery material of the present invention and preparation method thereof Attempt；
Fig. 3 is the electrochemistry loop test of embodiment 11 and comparative example five in battery material of the present invention and preparation method thereof Figure；
Fig. 4 is the electrochemistry loop test of embodiment 12 and comparative example six in battery material of the present invention and preparation method thereof Figure.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment one:
The present embodiment is using not alternating temperature in excessive lithium source, preparation process.
By (44.8g, 0.6mol) NiO, (16.6g, 0.2mol) Co2O3, (17.4g, 0.2mol) MnO2, (31.1g, 1.2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, is mixed Object is washed with deionized 3 times, obtains head product, and head product is 5 hours dry in 80 DEG C, is then placed in crucible, with 10 DEG C/ The heating rate of min is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then natural It is cooled to room temperature, obtains final product 1, structural formula LiNi0.6Co0.2Mn0.2O2。
Embodiment two:
The present embodiment is using alternating temperature in excessive lithium source, preparation process.
By (44.8g, 0.6mol) NiO, (16.6g, 0.2mol) Co2O3, (17.4g, 0.2mol) MnO2, (31.1g, 1.2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 1000 DEG C are heated to, is kept for 5 hours, then is cooled to 900 DEG C with the rate of temperature fall of 2 DEG C/min, is kept for 15 hours, with 2 DEG C/min Rate of temperature fall be cooled to 200 DEG C, then cooled to room temperature, mixture are washed with deionized 3 times, obtain head product, Head product is 5 hours dry in 80 DEG C, it is then placed in crucible, with the heating rate of 10 DEG C/min, is heated to 750 DEG C, keeps 10 hours, 200 DEG C is cooled to the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, obtains final product 2, structural formula is LiNi0.6Co0.2Mn0.2O2。
Embodiment three:
The present embodiment is using not alternating temperature in excessive lithium source, preparation process.
By (59.8g, 0.8mol) NiO, (8.3g, 0.1mol) Co2O3, (8.7g, 0.1mol) MnO2, (47.9g, 2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, is heated to It 780 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, mixture are spent Ion water washing 3 times, head product is obtained, head product is 5 hours dry in 80 DEG C, it is then placed in crucible, with 10 DEG C/min's Heating rate is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then naturally cools to Room temperature obtains final product 3, structural formula LiNi0.8Co0.1Mn0.1O2。
Example IV:
The present embodiment is using alternating temperature in excessive lithium source, preparation process.
By (59.8g, 0.8mol) NiO, (8.3g, 0.1mol) Co2O3, (8.7g, 0.1mol) MnO2, (47.9g, 2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, is heated to It 850 DEG C, is kept for 5 hours, then is cooled to 780 DEG C with the rate of temperature fall of 2 DEG C/min, kept for 15 hours, with the cooling speed of 2 DEG C/min Rate is cooled to 200 DEG C, then cooled to room temperature, and mixture is washed with deionized 3 times, head product is obtained, by head product It is 5 hours dry in 80 DEG C, it is then placed in crucible, with the heating rate of 10 DEG C/min, is heated to 750 DEG C, is kept for 10 hours, with The rate of temperature fall of 2 DEG C/min is cooled to 200 DEG C, then cooled to room temperature, obtains final product 4, and structural formula is LiNi0.8Co0.1Mn0.1O2。
Embodiment five:
The present embodiment is using alternating temperature in excessive lithium source, preparation process.
By (59.8g, 0.8mol) NiO, (8.3g, 0.1mol) Co2O3, (8.7g, 0.1mol) MnO2, (47.9g, 2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, is heated to It 900 DEG C, is kept for 5 hours, then is cooled to 780 DEG C with the rate of temperature fall of 2 DEG C/min, kept for 15 hours, with the cooling speed of 2 DEG C/min Rate is cooled to 200 DEG C, then cooled to room temperature, and mixture is washed with deionized 3 times, head product is obtained, by head product It is 5 hours dry in 80 DEG C, it is then placed in crucible, with the heating rate of 10 DEG C/min, is heated to 750 DEG C, is kept for 10 hours, with The rate of temperature fall of 2 DEG C/min is cooled to 200 DEG C, then cooled to room temperature, obtains final product 5, and structural formula is LiNi0.8Co0.1Mn0.1O2。
Embodiment six:
The present embodiment is using alternating temperature in excessive lithium source, preparation process.
By (59.8g, 0.8mol) NiO, (8.3g, 0.1mol) Co2O3(8.7g, 0.1mol) MnO2, (47.9g, 2mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, is heated to It 950 DEG C, is kept for 5 hours, then is cooled to 780 DEG C with the rate of temperature fall of 2 DEG C/min, kept for 15 hours, with the cooling speed of 2 DEG C/min Rate is cooled to 200 DEG C, then cooled to room temperature, and mixture is washed with deionized 3 times, head product is obtained, by head product It is 5 hours dry in 80 DEG C, it is then placed in crucible, with the heating rate of 10 DEG C/min, is heated to 750 DEG C, is kept for 10 hours, with The rate of temperature fall of 2 DEG C/min is cooled to 200 DEG C, then cooled to room temperature, obtains final product 6, and structural formula is LiNi0.8Co0.1Mn0.1O2。
Embodiment seven:
The present embodiment is using not alternating temperature in excessive lithium source, preparation process.
By (63.5g, 0.85mol) NiO, (8.3g, 0.1mol) Co2O3, (3.9g, 0.05mol) Al (OH)3, (59.8g, 2.5mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 780 DEG C are heated to, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, is mixed Object is washed with deionized 3 times, obtains head product, and head product is 5 hours dry in 80 DEG C, is then placed in crucible, with 10 DEG C/ The heating rate of min is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then natural It is cooled to room temperature, obtains final product 7, structural formula LiNi0.8Co0.1Mn0.1O2。
Embodiment eight:
The present embodiment is using alternating temperature in excessive lithium source, preparation process.
By (63.5g, 0.85mol) NiO, (8.3g, 0.1mol) Co2O3, (3.9g, 0.05mol) Al (OH)3, (59.8g, 2.5mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 5 hours, then is cooled to 750 DEG C with the rate of temperature fall of 2 DEG C/min, is kept for 15 hours, with 2 DEG C/min's Rate of temperature fall is cooled to 200 DEG C, then cooled to room temperature, and mixture is washed with deionized 3 times, obtains head product, will Head product is 5 hours dry in 80 DEG C, is then placed in crucible, with the heating rate of 10 DEG C/min, is heated to 750 DEG C, keeps 10 Hour, 200 DEG C are cooled to the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, obtain final product 8, structural formula is LiNi0.85Co0.1Al0.05O2。
Embodiment nine:
By 2.7g product 1(LiNi0.6Co0.2Mn0.2O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of 6 h of vacuum drying, The positive plate of coating material is obtained, cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbonic acid Methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
Embodiment ten:
By 2.7g product 2(LiNi0.6Co0.2Mn0.2O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of 6 h of vacuum drying, The positive plate of coating material is obtained, cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbonic acid Methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
Embodiment 11:
By 2.7g product 5(LiNi0.8Co0.1Mn0.1O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of 6 h of vacuum drying, The positive plate of coating material is obtained, cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbonic acid Methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
Embodiment 12:
By 2.7g product 8(LiNi0.85Co0.1Al0.05O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP are mixed into Even slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of vacuum drying 6 h obtain the positive plate of coating material, and cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC (methyl ethyl carbonate)=3/7 is assembled into 2032 button cells, surveys chemical property.
Comparative example one:
The present embodiment is using 1.1 times of lithium sources, not alternating temperature in preparation process.
By (44.8g, 0.6mol) NiO, (16.6g, 0.2mol) Co2O3, (17.4g, 0.2mol) MnO2(31.1g, 1.1mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, is mixed Object is washed with deionized 3 times, obtains head product, and head product is 5 hours dry in 80 DEG C, is then placed in crucible, with 10 DEG C/ The heating rate of min is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then natural It is cooled to room temperature, obtains final product 9, structural formula LiNi0.6Co0.2Mn0.2O2。
Comparative example two:
The present embodiment is using 1.1 times of lithium sources, not alternating temperature in preparation process.
By (59.8g, 0.8mol) NiO, (8.3g, 0.1mol) Co2O3, (8.7g, 0.1mol) MnO2, (31.1g, 1.1mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 780 DEG C are heated to, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, is mixed Object is washed with deionized 3 times, obtains head product, and head product is 5 hours dry in 80 DEG C, is then placed in crucible, with 10 DEG C/ The heating rate of min is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then natural It is cooled to room temperature, obtains final product 10, structural formula LiNi0.8Co0.1Mn0.1O2。
Comparative example three:
The present embodiment is using 1.1 times of lithium sources, not alternating temperature in preparation process.
By (63.5g, 0.85mol) NiO, (8.3g, 0.1mol) Co2O3, (3.9g, 0.05mol) Al (OH)3, (31.1g, 1.1mol) LiOH, (55.0g, 0.5mol) Li2SO4It is uniformly mixed, is put into corundum crucible, with the heating rate of 10 DEG C/min, 750 DEG C are heated to, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, is mixed Object is washed with deionized 3 times, obtains head product, and head product is 5 hours dry in 80 DEG C, is then placed in crucible, with 10 DEG C/ The heating rate of min is heated to 750 DEG C, is kept for 10 hours, is cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min, then natural It is cooled to room temperature, obtains final product 11, structural formula LiNi0.85Co0.1Al0.05O2。
Comparative example four:
By 2.7g product 9(LiNi0.6Co0.2Mn0.2O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of 6 h of vacuum drying, The positive plate of coating material is obtained, cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbonic acid Methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
Comparative example five:
By 2.7g product 10(LiNi0.8Co0.1Mn0.1O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry is coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, removes major part NMP, then 120 degree of 6 h of vacuum drying, The positive plate of coating material is obtained, cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbonic acid Methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
Comparative example six:
By 2.7g product 11(LiNi0.85Co0.1Al0.05O2), 0.15g conductive carbon, 0.15g PVDF, 3g NMP is mixed into uniformly Slurry, be coated on aluminium foil, first in 120 degrees Celsius of dry 10 min, remove major part NMP, be then dried in vacuo 6 for 120 degree H obtains the positive plate of coating material, and cathode uses lithium metal, and electrolyte is 1 M LiPF6-EC(ethylene carbonate)/EMC(carbon Sour methyl ethyl ester)=3/7,2032 button cells are assembled into, chemical property is surveyed.
One, elemental analysis is tested
Elemental composition is carried out to above-described embodiment product using inductive coupling plasma emission spectrograph (model: icap7600) Analysis, as shown in the table:
As can be seen from the table, if lithium salts and mole metering ratio of transition metal source are at 1.1 times, in the product being prepared The metering of lithium is compared less than 1, to lack lithium state, and when mole metering of lithium salts and transition metal source is than at 1.2 times or more, preparation The metering of the obtained lithium in product is compared greater than 1, is normal condition.Scarce lithium will affect the chemical property of product, show as holding Measure relatively low, cyclical stability variation.
Two, morphology observation
Imaging is carried out to producing 4,5 and 6 using scanning electron microscope.
Referring to Fig. 1, being the product 3(LiNi of fixed temperature preparation on the left of this figure0.8Co0.1Mn0.1O2), particle size master Will be between 0.5 ~ 1.2 micron, centre is the product 5(LiNi of 900 degree of alternating temperatures preparation0.8Co0.1Mn0.1O2), particle size is main Between 2 ~ 5 microns, right side is the product 6(LiNi of 950 degree of alternating temperatures preparation0.8Co0.1Mn0.1O2), particle size is mainly 5 ~ 12 Between micron, illustrate that temperature-switching method can effectively promote the single crystal size size of same material.
Three, particle size distribution test:
Using Malvern laser particle analyzer to the particle size and its distribution tests of material, the result is as follows:
By table as it can be seen that for same monocrystal material (LiNi0.6Co0.2Mn0.2O2), with the raising of thermostat temperature for the first time, grain Diameter becomes large-sized；In addition the size of the monocrystalline of all alternating temperatures preparation is all larger than the size of the monocrystalline of fixed temperature preparation.It is bigger Single crystal size facilitate promoted battery compacted density and volume energy density.
Four, to roller compaction density measurement
By product 1 and 2(LiNi0.6Co0.2Mn0.2O2), product 3 and 5(LiNi0.8Co0.1Mn0.1O2) and product 7 and 8 (LiNi0.85Co0.1Al0.05O2) anode pole piece is respectively prepared, compaction test is carried out with roll squeezer.
By table as it can be seen that after using multistage alternating temperature technology, monocrystalline LiNi0.6Co0.2Mn0.2O2Compacted density is from 3.1g/cm3Increase to 3.5 g/cm3, monocrystalline LiNi0.8Co0.1Mn0.1O2Compacted density is from 2.9 g/cm3Increase to 3.4 g/ cm3, monocrystalline LiNi0.85Co0.1Al0.05O2Compacted density is from 2.8g/ cm3Increase to 3.3 g/ cm3, higher compacted density has higher Volume energy density.
Five, electrochemistry loop test
The cyclical stability of material is tested with blue electric cell tester, test condition are as follows: the multiplying power of first 0.1C charges/puts Electricity circulation 3 times, then the multiplying power charge/discharge cycle of 1C 200 times.
As can be seen that the two kinds of nickel ion dopeds prepared using excessive lithium source (being greater than 1.2 times) from table, Fig. 2, Fig. 3 and Fig. 4 (LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2) and lithium nickel cobalt dioxide (LiNi0.85Co0.1Al0.05O2), actual specific capacity Obviously higher than the respective material of 1.1 times of lithium sources preparation, also obviously the former is better than the latter to the capacity retention ratio of 200 circulations, becomes The LiNi of warm therapy preparation0.6Co0.2Mn0.2O2The capacity retention ratio of material is better than the material of fixed temperature preparation, this may be with change Adiabator has smaller specific surface area, and surface side reaction is less related.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (10)

1. a kind of monocrystalline type battery material, which is characterized in that the monocrystalline type battery material be nickel-cobalt lithium manganate cathode material or Nickel cobalt lithium aluminate cathode material, the chemical formula of the nickel-cobalt lithium manganate cathode material are LiaNixCoyMnzO2, wherein 1.0≤a≤ The chemical formula of 1.1,0≤x≤1,0≤y≤1,0≤z≤1, and x+y+z=1, the nickel cobalt lithium aluminate cathode material is LibNiuCovAlwO2, wherein 1.0≤b≤1.1,0≤u≤1,0≤v≤1,0≤w≤1, and u+v+w=1.
2. the preparation method of monocrystalline type battery material according to claim 1, which is characterized in that including step are as follows: will contain Nickel compound, cobalt compound obtain monocrystalline type nickle cobalt lithium manganate containing manganese compound, excessive lithium source and inorganic fused salt mixed calcining Positive electrode, or nickel compound containing, cobalt compound, aluminum contained compound, excessive lithium source and inorganic fused salt mixed calcining are obtained Monocrystalline type nickel cobalt lithium aluminate cathode material, wherein the process of the calcining are as follows: with the heating rate of 10 DEG C/min, be heated to 1000 DEG C, it is kept for 5 hours, then be cooled to 900 DEG C with the rate of temperature fall of 2 DEG C/min, is kept for 15 hours, with the rate of temperature fall of 2 DEG C/min 200 DEG C are cooled to, then cooled to room temperature, obtain head product, head product is calcined again to obtain final product, it is described to forge again The process of burning are as follows: head product is 5 hours dry in 80 DEG C, then with the heating rate of 10 DEG C/min, 750 DEG C are heated to, keep 10 Hour, 200 DEG C are cooled to the rate of temperature fall of 2 DEG C/min, then cooled to room temperature, obtains final product.
3. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the nickel compound containing is Oxide NiO, hydroxide Ni (OH)2, nitrate Ni (NO3)2, oxalates NiC2O4One of or a variety of mixtures.
4. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the cobalt compound is Oxide CoO, oxide Co2O3, hydroxide Co (OH)2, nitrate Co (NO3)2, oxalates CoC2O4One of or it is a variety of Mixture.
5. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that described to be containing manganese compound Oxide M nO, oxide M nO2, hydroxide Mn (OH)2, nitrate Mn (NO3)2, oxalates MnC2O4One of or it is a variety of Mixture.
6. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the aluminum contained compound is Oxide Al2O3, hydroxide Al (OH)3, nitrate Al (NO3)3, oxalates Al2 (C2O4)3One of or a variety of mixing Object.
7. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the lithium source be LiOH, LiNO3、Li2CO3One of or a variety of mixtures.
8. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the lithium source contains with described Nickel compound, the cobalt compound, the summation containing manganese compound molar ratio >=1.2；The lithium source and nickeliferousization Close object, the cobalt compound, the aluminum contained compound summation molar ratio >=1.2.
9. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that the inorganic fused salt is Li2SO4、Na2SO4、K2SO4、Rb2SO4、Cs2SO4、LiF、LiCl、NaCl、KCl、RbCl、CsCl、BaCl2、CaCl、Li2CO3、 Na2CO3、K2CO3、LiNO3、NaNO3, one of LiOH, NaOH, KOH or a variety of mixtures, mixed proportion, which can be, arbitrarily rubs You measure ratio.
10. the preparation method of monocrystalline type battery material according to claim 2, which is characterized in that described to be mixed into dry method Grinding, wet grinding, dry ball milling or wet ball grinding.
CN201910609435.9A 2019-07-08 2019-07-08 A kind of monocrystalline type battery material and preparation method thereof Pending CN110336007A (en)

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Application publication date: 20191015