CN107369836B - Cathode material, preparation method thereof and lithium ion battery containing cathode material - Google Patents

Cathode material, preparation method thereof and lithium ion battery containing cathode material Download PDF

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CN107369836B
CN107369836B CN201710663649.5A CN201710663649A CN107369836B CN 107369836 B CN107369836 B CN 107369836B CN 201710663649 A CN201710663649 A CN 201710663649A CN 107369836 B CN107369836 B CN 107369836B
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CN107369836A (en
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吴苗
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SHUANGYILI (NINGBO) BATTERY 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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 discloses a positive electrode material, a preparation method thereof and lithium ion containing the positive electrode material, wherein the positive electrode material comprises the following raw materials in parts by weight: 85-92 parts of nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 0.4-0.8 part of activated graphene, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene-based bis-stearamide, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer, wherein the positive electrode material is prepared by the steps of preparation of activated graphene, emulsification and dispersion, viscosity regulation and the like. The lithium ion battery prepared by the anode material provided by the invention has excellent high and low temperature performance and cycle performance, and the lithium ion battery provided by the invention is worthy of popularization and application.

Description

Cathode material, preparation method thereof and lithium ion battery containing cathode material
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of batteries, and particularly relates to a positive electrode material, a preparation method thereof and lithium ion containing the positive electrode material.
[ background of the invention ]
In recent years, with the rapid development of the lithium battery industry, lithium ion batteries are beginning to enter the application fields of electric vehicles and large mobile power supplies, but lead-acid batteries still occupy a leading position at present. The anode material of the lithium ion battery is usually lithium cobaltate, lithium manganate, lithium nickelate and various transition metal oxides doped with other elements, but has a lot of problems and can not meet the development requirements of electric vehicles and large-scale mobile power supplies.
Lithium ion battery electrolytes occupy a very important position in lithium ion batteries, and directly affect the electrical performance of the lithium ion batteries. The electrolyte of the present lithium ion battery mainly comprises electrolyte salt and solvent, wherein the solvent generally adopts carbonate mixed solvent such as ethylene carbonate EC, propylene carbonate PC, ethylene carbonate EMC, propylene carbonate DMC, diethyl carbonate DEC, etc., and the commonly used electrolyte salt is lithium hexafluorophosphate LiPF6。
The lithium ion battery has the advantages of high voltage platform, no memory performance and the like, and is widely applied. But at the same time, the application range of the lithium ion battery is limited by some conditions, such as the applied environment temperature is one of the important factors. And the cycle performance of the lithium manganate battery is poor at present, and needs to be further improved.
[ summary of the invention ]
The invention aims to solve the technical problems that the high-temperature and low-temperature cycle performance of a lithium ion battery prepared by adopting the conventional anode material and electrolyte is not ideal enough, the high-temperature effect is poor, the requirement of the lithium ion battery cannot be met and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the positive electrode material comprises the following raw materials in parts by weight: 85-92 parts of nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 0.4-0.8 part of activated graphene, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene-based bis-stearamide, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
s1: stirring the graphene for 20-45min at the magnetic field intensity of 4500-6000GS, the ultrasonic power of 200-550W, the temperature of 42-55 ℃ and the rotating speed of 200-300r/min to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 3-8:1, and activating for 1.2-2.5h at the temperature of 50-72 ℃ and the rotating speed of 100-150r/min to prepare activated graphene;
s3: adding 0.4-0.8 part of the activated graphene prepared in the step S2, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene bis stearamide and 300 parts of water 210 into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 2-3h to prepare a mixture A;
s4: adding 85-92 parts of powder nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4-4.5 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 3500-5500m Pa.s by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
The invention also provides a lithium ion battery containing the anode material, which comprises an electrode group and lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises an anode, a cathode and a diaphragm, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 3-8 parts of lithium hexafluorophosphate, 42-60 parts of diethyl carbonate, 12-20 parts of propylene carbonate, 10-18 parts of ethylene carbonate, 7-14 parts of dipropyl carbonate, 9-16 parts of ethyl formate, 0.5-0.8 part of graphene and 0.4-0.6 part of additive A;
the additive A comprises the following raw materials in parts by weight: 10-18 parts of tributyrin and 2-3 parts of polyoxyethylene-polyoxypropylene copolymer.
Further, the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.5-0.9 part of additive B, wherein the additive B comprises the following raw materials in parts by weight: 9-16 parts of diacetic acid-1, 4-cyclohexanediol ester and 1-2 parts of polydimethylsiloxane.
Further, the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.1-0.2 part of additive C, wherein the additive C comprises the following raw materials in parts by weight: 15-20 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 6-12 parts of gluconolactone.
Further, the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.2-0.4 part of additive D, wherein the additive D comprises the following raw materials in parts by weight: 5-9 parts of 2, 3-butanedione and 3-6 parts of dimethyl diketone.
The invention has the following beneficial effects:
(1) it can be seen from the data of example 3 and comparative examples 1 to 5 that the activated graphene, ketjen black, the ethylene-vinyl acetate copolymer, and the ethylene-based bis-stearamide are simultaneously added to prepare the cathode material, and the activated graphene, ketjen black, the ethylene-vinyl acetate copolymer, and the ethylene-based bis-stearamide produce a synergistic effect in the battery prepared from the cathode material, so that the high-temperature and low-temperature performance and the cycle performance of the lithium ion battery are remarkably improved.
(2) The functions of the graphene, the additive A, the additive B, the additive C and the additive D are respectively as follows:
1) the graphene can improve the performance of the lithium ion battery;
2) the addition of the additive A reduces the surface tension of the electrolyte of the lithium ion secondary battery, effectively improves the adsorption and infiltration of the positive and negative pole pieces and the diaphragm to the electrolyte, enables the electrolyte to quickly reach a stable and uniform state in the battery, and can prolong the cycle life of the lithium ion battery.
3) The additive B forms a layer of protective film on the surface of the positive electrode in the first charging process, reduces the decomposition and gas generation of electrolyte on the surface of the positive electrode, and can inhibit Mn from positive electrode active substances in the subsequent charging and discharging processes2+The dissolution of the ions improves the high-temperature performance of the lithium manganate battery.
4) The additive C can improve the low-temperature performance of the electrolyte of the lithium ion battery, the oxalic acid di (butoxy ethoxy ethyl) ester and the gluconolactone are selected as the preparation raw materials of the additive C which can reduce the temperature, the decomposition voltage of the electrolyte can be effectively improved after the additive C is added into the electrolyte, a passive film can be formed on the surface of the composite graphite cathode, the composite graphite cathode has better oxidation stability to the anode, the working performance of the electrolyte at low temperature is effectively improved, and the overall time life of the lithium ion battery is prolonged (namely the storage service life of the battery is prolonged);
5) the additive D can be complexed with lithium ions for ion transmission, so that acidic substances generated by hydrolysis of lithium hexafluorophosphate in an electrolyte system of the lithium ion battery can be eliminated, and the performance of the lithium ion battery is improved.
It can be seen from the data of example 3 and comparative examples 6 to 11 that the graphene, the additive a, the additive B, the additive C and the additive D are simultaneously added to prepare the electrolyte of the lithium ion battery, and the graphene, the additive a, the additive B, the additive C and the additive D generate a synergistic effect in the battery prepared from the above electrolytes, so that the high-temperature and low-temperature performance and the cycle performance of the lithium ion battery are remarkably improved.
(3) The lithium ion battery prepared by the anode material and the lithium ion battery electrolyte provided by the invention has excellent high and low temperature performance and cycle performance, and the lithium ion battery provided by the invention is worthy of popularization and application.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the cathode material comprises the following raw materials in parts by weight: 85-92 parts of nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 0.4-0.8 part of activated graphene, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene-based bis-stearamide, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer.
The preparation method of the cathode material comprises the following steps:
s1: stirring the graphene for 20-45min at the magnetic field intensity of 4500-6000GS, the ultrasonic power of 200-550W, the temperature of 42-55 ℃ and the rotating speed of 200-300r/min to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 3-8:1, and activating for 1.2-2.5h at the temperature of 50-72 ℃ and the rotating speed of 100-150r/min to prepare activated graphene;
s3: adding 0.4-0.8 part of the activated graphene prepared in the step S2, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene bis stearamide and 300 parts of water 210 into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 2-3h to prepare a mixture A;
s4: adding 85-92 parts of powder nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4-4.5 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 3500-5500m Pa.s by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
The lithium ion battery containing the anode material comprises an electrode group and lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises an anode, a cathode and a diaphragm, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 3-8 parts of lithium hexafluorophosphate, 42-60 parts of diethyl carbonate, 12-20 parts of propylene carbonate, 10-18 parts of ethylene carbonate, 7-14 parts of dipropyl carbonate, 9-16 parts of ethyl formate, 0.5-0.8 part of graphene, 0.4-0.6 part of additive A, 0.5-0.9 part of additive B, 0.1-0.2 part of additive C and 0.2-0.4 part of additive D.
The additive A comprises the following raw materials in parts by weight: 10-18 parts of tributyrin and 2-3 parts of polyoxyethylene-polyoxypropylene copolymer.
The additive B comprises the following raw materials in parts by weight: 9-16 parts of diacetic acid-1, 4-cyclohexanediol ester and 1-2 parts of polydimethylsiloxane.
The additive C comprises the following raw materials in parts by weight: 15-20 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 6-12 parts of gluconolactone.
The additive D comprises the following raw materials in parts by weight: 5-9 parts of 2, 3-butanedione and 3-6 parts of dimethyl diketone.
The present invention is illustrated by the following more specific examples.
Example 1
The positive electrode material comprises the following raw materials in parts by weight: 90 parts of nickel cobalt lithium manganate, 1.6 parts of boron fiber, 2.5 parts of silicon nitride, 0.6 part of activated graphene, 1 part of Ketjen black, 3 parts of ethylene-vinyl acetate copolymer, 0.8 part of ethylene-based bis-stearamide, 1.5 parts of chlorinated polyethylene and 0.5 part of fatty acid stabilizer.
The preparation method of the cathode material comprises the following steps:
s1: stirring graphene for 32min under the conditions that the magnetic field intensity is 5500GS, the ultrasonic power is 40W, the temperature is 50 ℃, and the rotating speed is 250r/min, so as to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 6:1, and activating for 2 hours at the temperature of 65 ℃ and the rotating speed of 130r/min to prepare activated graphene;
s3: adding 0.4-0.8 part of activated graphene prepared in the step S2, 1 part of Ketjen black, 3 parts of ethylene-vinyl acetate copolymer, 0.8 part of ethylene-based bis-stearamide and 260 parts of water into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 2.5 hours to prepare a mixture A;
s4: adding 90 parts of powder nickel cobalt lithium manganate, 1.6 parts of boron fiber, 2.5 parts of silicon nitride, 1.5 parts of chlorinated polyethylene and 0.5 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4.3 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 4000m Pa & S by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
The lithium ion battery containing the anode material comprises an electrode group and lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises an anode, a cathode and a diaphragm, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 6 parts of lithium hexafluorophosphate, 50 parts of diethyl carbonate, 16 parts of propylene carbonate, 15 parts of ethylene carbonate, 10 parts of dipropyl carbonate, 12 parts of ethyl formate, 0.7 part of graphene, 0.5 part of additive A, 0.7 part of additive B, 0.1 part of additive C and 0.3 part of additive D.
The additive A comprises the following raw materials in parts by weight: 15 parts of tributyrin and 2.5 parts of polyoxyethylene-polyoxypropylene copolymer.
The additive B comprises the following raw materials in parts by weight: 13 parts of 1, 4-cyclohexanediol diacetate and 1.5 parts of polydimethylsiloxane.
The additive C comprises the following raw materials in parts by weight: 18 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 9 parts of gluconolactone.
The additive D comprises the following raw materials in parts by weight: 8 parts of 2, 3-butanedione and 5 parts of dimethyl diketone.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the embodiment and installing the anode made of the anode material of the embodiment in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells by a conventional method to obtain the lithium ion battery.
Example 2
The positive electrode material comprises the following raw materials in parts by weight: 86 parts of nickel cobalt lithium manganate, 1 part of boron fiber, 2 parts of silicon nitride, 0.4 part of activated graphene, 0.6 part of Ketjen black, 2 parts of ethylene-vinyl acetate copolymer, 0.5 part of ethylene-based bis-stearamide, 1.2 parts of chlorinated polyethylene and 0.4 part of fatty acid stabilizer.
The preparation method of the cathode material comprises the following steps:
s1: stirring graphene for 45min at the magnetic field intensity of 4500GS, the ultrasonic power of 200W, the temperature of 42 ℃ and the rotating speed of 200r/min to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 3:1, and activating for 2.5 hours at the temperature of 50 ℃ and the rotating speed of 100r/min to prepare activated graphene;
s3: adding 0.4 part of activated graphene prepared in the step S2, 0.6 part of Ketjen black, 2 parts of ethylene-vinyl acetate copolymer, 0.5 part of ethylene-based bis-stearamide and 210 parts of water into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 3 hours to prepare a mixture A;
s4: adding 86 parts of powder nickel cobalt lithium manganate, 1 part of boron fiber, 2 parts of silicon nitride, 1.2 parts of chlorinated polyethylene and 0.4 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4.5 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 3500 mPa & S by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
The lithium ion battery containing the anode material comprises an electrode group and lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises an anode, a cathode and a diaphragm, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 3 parts of lithium hexafluorophosphate, 42 parts of diethyl carbonate, 12 parts of propylene carbonate, 10 parts of ethylene carbonate, 7 parts of dipropyl carbonate, 9 parts of ethyl formate, 0.5 part of graphene, 0.4 part of additive A, 0.5 part of additive B, 0.1 part of additive C and 0.2 part of additive D.
The additive A comprises the following raw materials in parts by weight: 10 parts of tributyrin and 2 parts of polyoxyethylene-polyoxypropylene copolymer.
The additive B comprises the following raw materials in parts by weight: 9 parts of diacetic acid-1, 4-cyclohexanediol ester and 1 part of polydimethylsiloxane.
The additive C comprises the following raw materials in parts by weight: 15 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 6 parts of gluconolactone.
The additive D comprises the following raw materials in parts by weight: 5 parts of 2, 3-butanedione and 3 parts of dimethyl diketone.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the embodiment and installing the anode made of the anode material of the embodiment in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells by a conventional method to obtain the lithium ion battery.
Example 3
The positive electrode material comprises the following raw materials in parts by weight: 90 parts of nickel cobalt lithium manganate, 2 parts of boron fiber, 3 parts of silicon nitride, 0.8 part of activated graphene, 1.3 parts of Ketjen black, 4 parts of ethylene-vinyl acetate copolymer, 1 part of ethylene-based bis-stearamide, 1.8 parts of chlorinated polyethylene and 0.6 part of fatty acid stabilizer.
The preparation method of the cathode material comprises the following steps:
s1: stirring graphene for 20min at the magnetic field intensity of 6000GS, the ultrasonic power of 550W, the temperature of 55 ℃ and the rotating speed of 300r/min to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 8:1, and activating for 1.2h at the temperature of 72 ℃ and the rotating speed of 150r/min to prepare activated graphene;
s3: adding 0.8 part of activated graphene prepared in the step S2, 1.3 parts of Ketjen black, 4 parts of ethylene-vinyl acetate copolymer, 1 part of ethylene-based bis-stearamide and 300 parts of water into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 2-3 hours to prepare a mixture A;
s4: adding 90 parts of powder nickel cobalt lithium manganate, 2 parts of boron fiber, 3 parts of silicon nitride, 1.8 parts of chlorinated polyethylene and 0.6 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 5500m Pa & S by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
The lithium ion battery containing the anode material comprises an electrode group and lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises an anode, a cathode and a diaphragm, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 8 parts of lithium hexafluorophosphate, 60 parts of diethyl carbonate, 20 parts of propylene carbonate, 18 parts of ethylene carbonate, 14 parts of dipropyl carbonate, 16 parts of ethyl formate, 0.8 part of graphene, 0.6 part of additive A, 0.9 part of additive B, 0.2 part of additive C and 0.4 part of additive D.
The additive A comprises the following raw materials in parts by weight: 18 parts of tributyrin and 3 parts of polyoxyethylene-polyoxypropylene copolymer.
The additive B comprises the following raw materials in parts by weight: 16 parts of 1, 4-cyclohexanediol diacetate and 2 parts of polydimethylsiloxane.
The additive C comprises the following raw materials in parts by weight: 20 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 12 parts of gluconolactone.
The additive D comprises the following raw materials in parts by weight: 9 parts of 2, 3-butanedione and 6 parts of dimethyl diketone.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the embodiment and installing the anode made of the anode material of the embodiment in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells by a conventional method to obtain the lithium ion battery.
Comparative example 1
The only differences compared to example 3 are: the raw materials for preparing the anode material lack activated graphene, Ketjen black, ethylene-vinyl acetate copolymer and ethylene-based bis-stearamide.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 2
The only differences compared to example 3 are: the raw materials for preparing the cathode material lack activated graphene.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 3
The only differences compared to example 3 are: ketjen black is absent in the raw materials for preparing the cathode material.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 4
The only differences compared to example 3 are: the raw materials for preparing the cathode material lack ethylene-vinyl acetate copolymer.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 5
The only differences compared to example 3 are: the raw materials for preparing the cathode material lack ethylene-based bis-stearamide.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 6
The only differences compared to example 3 are: the raw materials for preparing the lithium ion battery electrolyte are lack of graphene, an additive A, an additive B, an additive C and an additive D.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 7
The only differences compared to example 3 are: graphene is absent in the raw materials for preparing the lithium ion battery electrolyte.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 8
The only differences compared to example 3 are: the raw materials for preparing the lithium ion battery electrolyte lack additive A.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 9
The only differences compared to example 3 are: the raw materials for preparing the lithium ion battery electrolyte lack additive B.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 10
The only differences compared to example 3 are: the raw materials for preparing the lithium ion battery electrolyte lack additive C.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
Comparative example 11
The only differences compared to example 3 are: the raw materials for preparing the lithium ion battery electrolyte lack additive D.
Randomly extracting 20 cells which are not injected with liquid 1665132, respectively injecting the 20 cells into the electrolyte of the lithium ion battery provided by the comparative example and installing the anode made of the anode material of the comparative example in a constant temperature and humidity room, and aging, forming, degassing, sealing and grading the injected cells according to a conventional method to obtain the lithium ion battery.
For comparison, the liquid-filled batteries used in examples 1 to 3 and comparative examples 1 to 11 all refer to the same batch (1665132S) of batteries, and the same batch refers to the same batch of batteries produced by the same process except that the mounted positive electrode is different or the electrolyte injected in the liquid-filling process is different. In this type of cell, the negative electrode is composite graphite.
The lithium ion batteries manufactured in examples 1 to 3 and comparative examples 1 to 11 were subjected to high temperature 55 ℃ and 1C discharge, high temperature 20 ℃ and 1C discharge, high temperature 35 ℃ and 0.2C discharge, normal temperature (25 ℃)1C cycle test, and high temperature 55 ℃ and 1C cycle test, respectively, and the test results are shown in the following tables.
Figure BDA0001371225360000111
Figure BDA0001371225360000121
From the above table, it can be seen that: (1) the test results in the table show that the lithium ion battery prepared by the anode material provided by the invention has excellent high and low temperature performance and cycle performance.
(2) It can be seen from the data of example 3 and comparative examples 1 to 5 that the activated graphene, ketjen black, the ethylene-vinyl acetate copolymer, and the ethylene-based bis-stearamide are simultaneously added to prepare the cathode material, and the activated graphene, ketjen black, the ethylene-vinyl acetate copolymer, and the ethylene-based bis-stearamide produce a synergistic effect in the battery prepared from the cathode material, so that the high-temperature and low-temperature performance and the cycle performance of the lithium ion battery are remarkably improved.
(3) The test results in the table show that the lithium ion battery prepared by the lithium ion battery electrolyte provided by the invention has excellent high and low temperature performance and cycle performance.
(4) The functions of the graphene, the additive A, the additive B, the additive C and the additive D are respectively as follows:
1) the graphene can improve the performance of the lithium ion battery;
2) the addition of the additive A reduces the surface tension of the electrolyte of the lithium ion secondary battery, effectively improves the adsorption and infiltration of the positive and negative pole pieces and the diaphragm to the electrolyte, enables the electrolyte to quickly reach a stable and uniform state in the battery, and can prolong the cycle life of the lithium ion battery.
3) The additive B forms a layer of protective film on the surface of the positive electrode in the first charging process, reduces the decomposition and gas generation of electrolyte on the surface of the positive electrode, and can inhibit Mn from positive electrode active substances in the subsequent charging and discharging processes2+The dissolution of the ions improves the high-temperature performance of the lithium manganate battery.
4) The additive C can improve the low-temperature performance of the electrolyte of the lithium ion battery, the oxalic acid di (butoxy ethoxy ethyl) ester and the gluconolactone are selected as the preparation raw materials of the additive C which can reduce the temperature, the decomposition voltage of the electrolyte can be effectively improved after the additive C is added into the electrolyte, a passive film can be formed on the surface of the composite graphite cathode, the composite graphite cathode has better oxidation stability to the anode, the working performance of the electrolyte at low temperature is effectively improved, and the overall time life of the lithium ion battery is prolonged (namely the storage service life of the battery is prolonged);
5) the additive D can be complexed with lithium ions for ion transmission, so that acidic substances generated by hydrolysis of lithium hexafluorophosphate in an electrolyte system of the lithium ion battery can be eliminated, and the performance of the lithium ion battery is improved.
It can be seen from the data of example 3 and comparative examples 6 to 11 that the graphene, the additive a, the additive B, the additive C and the additive D are simultaneously added to prepare the electrolyte of the lithium ion battery, and the graphene, the additive a, the additive B, the additive C and the additive D generate a synergistic effect in the battery prepared from the above electrolytes, so that the high-temperature and low-temperature performance and the cycle performance of the lithium ion battery are remarkably improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. The positive electrode material is characterized by comprising the following raw materials in parts by weight: 85-92 parts of nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 0.4-0.8 part of activated graphene, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene-based bis-stearamide, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer;
the preparation method of the activated graphene comprises the following steps:
stirring the graphene for 20-45min at the magnetic field intensity of 4500-6000GS, the ultrasonic power of 200-550W, the temperature of 42-55 ℃ and the rotating speed of 200-300r/min to prepare graphene energy powder;
adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 3-8:1, and activating for 1.2-2.5h at the temperature of 50-72 ℃ and the rotating speed of 100-plus-material 150r/min to prepare the activated graphene.
2. A method for producing the positive electrode material according to claim 1, comprising the steps of:
s1: stirring the graphene for 20-45min at the magnetic field intensity of 4500-6000GS, the ultrasonic power of 200-550W, the temperature of 42-55 ℃ and the rotating speed of 200-300r/min to prepare graphene energy powder;
s2: adding sodium hexadecylbenzene sulfonate into the graphene energy powder prepared in the step S1, wherein the mass ratio of the graphene energy powder to the sodium hexadecylbenzene sulfonate is 3-8:1, and activating for 1.2-2.5h at the temperature of 50-72 ℃ and the rotating speed of 100-150r/min to prepare activated graphene;
s3: adding 0.4-0.8 part of the activated graphene prepared in the step S2, 0.6-1.3 parts of Ketjen black, 2-4 parts of ethylene-vinyl acetate copolymer, 0.5-1 part of ethylene bis stearamide and 300 parts of water 210 into a high-shear dispersion emulsifying machine for emulsifying and dispersing for 2-3h to prepare a mixture A;
s4: adding 85-92 parts of powder nickel cobalt lithium manganate, 1-2 parts of boron fiber, 2-3 parts of silicon nitride, 1.2-1.8 parts of chlorinated polyethylene and 0.4-0.6 part of fatty acid stabilizer into the mixture A prepared in the step S3, and continuing emulsifying and dispersing for 4-4.5 hours to prepare a mixture B;
s5: adjusting the viscosity of the mixture B prepared in the step S4 to 3500-5500m Pa.s by using water to prepare anode slurry;
s6: and (4) processing the positive electrode slurry prepared in the step (S5) to prepare a positive electrode material.
3. A lithium ion battery containing the cathode material of claim 1, which is characterized by comprising an electrode group and a lithium ion battery electrolyte, wherein the electrode group and the lithium ion battery electrolyte are sealed in a battery shell, the electrode group comprises a cathode, an anode and a separator, and the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 3-8 parts of lithium hexafluorophosphate, 42-60 parts of diethyl carbonate, 12-20 parts of propylene carbonate, 10-18 parts of ethylene carbonate, 7-14 parts of dipropyl carbonate, 9-16 parts of ethyl formate, 0.5-0.8 part of graphene and 0.4-0.6 part of additive A;
the additive A comprises the following raw materials in parts by weight: 10-18 parts of tributyrin and 2-3 parts of polyoxyethylene-polyoxypropylene copolymer;
the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.5-0.9 part of additive B, wherein the additive B comprises the following raw materials in parts by weight: 9-16 parts of diacetic acid-1, 4-cyclohexanediol ester and 1-2 parts of polydimethylsiloxane;
the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.1-0.2 part of additive C, wherein the additive C comprises the following raw materials in parts by weight: 15-20 parts of oxalic acid di (butoxy ethoxy ethyl) ester and 6-12 parts of gluconolactone;
the lithium ion battery electrolyte comprises the following raw materials in parts by weight: 0.2-0.4 part of additive D, wherein the additive D comprises the following raw materials in parts by weight: 5-9 parts of 2, 3-butanedione and 3-6 parts of dimethyl diketone.
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