CN113471435A - Lithium ion battery cathode material and preparation method thereof - Google Patents

Lithium ion battery cathode material and preparation method thereof Download PDF

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Publication number
CN113471435A
CN113471435A CN202110553794.4A CN202110553794A CN113471435A CN 113471435 A CN113471435 A CN 113471435A CN 202110553794 A CN202110553794 A CN 202110553794A CN 113471435 A CN113471435 A CN 113471435A
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parts
lithium ion
ion battery
stirring
negative electrode
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吴秋丽
张凯
马斌
陈杰
杨山
李载波
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Huizhou Liwinon Energy Technology Co Ltd
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Huizhou Liwinon 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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery cathode material and a preparation method thereof, wherein the lithium ion battery cathode material comprises the following raw materials in parts by weight: 30-50 parts of active substance, 0.01-1.5 parts of conductive agent, 0.01-2 parts of wetting agent, 1.0-2.5 parts of binder, 0.1-5 parts of deionized water and 0.1-1.0 part of thickening agent. According to the lithium ion battery cathode material, the impregnating compound is added, the phenomenon of lithium precipitation of the cathode plate of the battery in a low-temperature environment is improved, the unique porous structure of the impregnating compound can promote lithium ion transmission, and the problem of black spots on a circulating interface is further improved.

Description

Lithium ion battery cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery cathode material and a preparation method thereof.
Background
With the development of economy, people's awareness of environmental protection is gradually strengthened, and lithium ion batteries, which are clean energy, are widely used in consumer electronics. However, when the lithium ion battery works in a low-temperature environment, the situation of lithium precipitation of the negative electrode plate often occurs, which causes the capacity of the battery to be rapidly reduced and unrecoverable, not only affects the service life of the battery, but also brings great potential safety hazards.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the lithium ion battery cathode material is provided, the phenomenon of lithium precipitation of the cathode plate of the battery in a low-temperature environment is improved by adding the impregnating compound, and the unique porous structure of the impregnating compound can promote lithium ion transmission, so that the problem of black spots on a circulating interface is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium ion battery cathode material comprises the following raw materials in parts by weight: 30-50 parts of active substance, 0.01-1.5 parts of conductive agent, 0.01-2 parts of wetting agent, 1.0-2.5 parts of binder, 0.1-10 parts of deionized water and 0.1-1.0 part of thickening agent.
Preferably, the lithium ion battery negative electrode material comprises the following raw materials in parts by weight: 40-50 parts of active substance, 0.1-1.5 parts of conductive agent, 0.1-2 parts of wetting agent, 1.5-2.5 parts of binder, 0.2-6 parts of deionized water and 0.2-0.5 part of thickening agent.
Preferably, the active substance is one or more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composites, lithium titanate carbon composites, silicon carbon or silicon oxygen materials.
Preferably, the conductive agent is one or more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
Preferably, the binder is one or a mixture of more of styrene butadiene rubber, styrene-acrylic, carboxymethyl cellulose, polyacrylic acid and polytetrafluoroethylene, and the solid content of the binder is 6-40%.
Preferably, the impregnating compound is an oxide of a third main group or a fourth main group, the pore diameter of the impregnating compound is 10-100 nm, and the solid content is 5-20%.
Preferably, the thickening agent is one or a mixture of sodium carboxymethyl cellulose and lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1% -2%.
Another object of the present invention is to: aiming at the defects of the prior art, the preparation method of the lithium ion battery cathode material is provided, the preparation process is simple and easy to implement, the cost is lower, and the service life and the use safety of the battery are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
Preferably, the stirring speed in the step (A) is 100-500 r/min; in the step (B), the stirring speed is 200-600 r/min, and the stirring temperature is 20-30 ℃; in the step (C), the stirring speed is 100-300 r/min, and the stirring temperature is 20-30 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.08 mpa to-0.1 mpa.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the phenomenon of lithium precipitation of the negative electrode plate of the battery in a low-temperature environment is improved by adding the impregnating compound, and the unique porous structure of the impregnating compound can promote lithium ion transmission, so that the problem of black spots on a circulating interface is solved.
Drawings
FIG. 1 is a graph comparing example 1 of the present invention and comparative example 1 after charge and discharge at a low temperature of-10 ℃ and 0.7C rate cycle.
Fig. 2 is a comparison graph of example 1 of the present invention and comparative example 1 after 300 times of charge and discharge at a rate of 1C at room temperature.
Detailed Description
1. The lithium ion battery cathode material comprises the following raw materials in parts by weight: 30-50 parts of active substance, 0.01-1.5 parts of conductive agent, 0.01-2 parts of wetting agent, 1.0-2.5 parts of binder, 0.1-10 parts of deionized water and 0.1-1.0 part of thickening agent.
According to the invention, the impregnating compound is added, so that the lithium precipitation phenomenon of the negative electrode plate of the battery under a low-temperature environment (minus 10-10 ℃) is improved, and the unique porous structure of the impregnating compound can promote lithium ion transmission, thereby improving the problem of black spots on a circulating interface.
Preferably, the lithium ion battery negative electrode material comprises the following raw materials in parts by weight: 40-50 parts of active substance, 0.1-1.5 parts of conductive agent, 0.1-2 parts of wetting agent, 1.5-2.5 parts of binder, 0.2-6 parts of deionized water and 0.2-0.5 part of thickening agent.
Preferably, the active substance is one or more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composites, lithium titanate carbon composites, silicon carbon or silicon oxygen materials.
Preferably, the conductive agent is one or more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
Preferably, the binder is one or a mixture of more of styrene butadiene rubber, styrene-acrylic, carboxymethyl cellulose, polyacrylic acid and polytetrafluoroethylene, and the solid content of the binder is 6-40%.
Preferably, the impregnating compound is an oxide of a third main group or a fourth main group, the pore diameter of the impregnating compound is 10-100 nm, and the solid content is 5-20%. The third main group oxide comprises boron oxide, aluminum oxide, gallium oxide, indium oxide, thallium oxide and the like, the fourth main group oxide comprises silicon oxide, germanium dioxide, tin oxide, lead oxide and the like, and the impregnating compound adopts the main group oxide with a continuous three-dimensional pore structure, so that an ion channel can be improved for the slurry, lithium ion transmission is promoted, and the problem of interface black spots is solved. The pore diameter of the impregnating compound can be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm and 100nm, the lithium ion transmission channel is easy to block when the pore diameter of the impregnating compound is too small, and the mechanical strength is not enough when the pore diameter of the impregnating compound is too large; the solid content of the impregnating compound can be 5%, 8%, 10%, 12%, 15%, 18% and 20%, the solid content of the impregnating compound is too low and insufficient in impregnation, and the solid content of the impregnating compound is too high, so that the thickness is too thick, and the lithium ion transmission distance is increased.
Preferably, the thickening agent is one or a mixture of sodium carboxymethyl cellulose and lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1% -2%. If the solid content of the thickener is too low, the slurry is easy to be unstable, and if the solid content of the thickener is too high, the coating thickness is easy to be thickened, so that the lithium ion transmission resistance is increased. The solids content of the thickener may be 1%, 1.5% or 2%.
2. A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
The preparation method comprises the steps of stirring the conductive agent difficult to disperse in advance, adding the thickening agent twice, wherein the first addition can enable the slurry to be dispersed more uniformly, shearing the slurry, kneading, and the second addition mainly comprises the steps of keeping the slurry stable and adjusting the viscosity of the slurry, and then adding the binder to avoid demulsification caused by long-time stirring of the binder, so that the pole piece has poor cohesiveness, and the prepared lithium ion battery negative electrode material is uniform and good in stability. The preparation method has great influence on the quality of the cathode material, when the conductive agent is not stirred and dispersed in advance, the conductive agent is easy to agglomerate in the slurry, when the thickening agent is not added in batches according to needs, the conductive agent is easy to be distributed unevenly, so that the slurry is unstable, and when the binder is stirred too early, the binder is easy to break emulsion in the stirring process to cause failure and the cohesiveness is ineffective. Preferably, the conductive agent is added, mixed and stirred for 30min, the scraping is carried out once in 15min, the thickening agent is added, mixed and stirred for 30min, and the scraping is carried out once in 15 min; adding the rest thickening agent, stirring for 60min, adding the impregnating compound, and stirring for 60 min. The frictioning helps to better disperse the raw materials in the slurry. Finally, the viscosity of the slurry is controlled to be 1000-6000mPa.s, the viscosity is too high, the coating process is difficult, and the problem of slurry leveling exists; the viscosity is too low, the slurry is easy to settle, the stability of the slurry is poor, and the slurry is easy to stick to a roller during rolling.
Preferably, the stirring speed in the step (A) is 100-500 r/min; in the step (B), the stirring speed is 200-600 r/min, and the stirring temperature is 20-30 ℃; in the step (C), the stirring speed is 100-300 r/min, and the stirring temperature is 20-30 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.08 mpa to-0.1 mpa. The vacuum pumping helps to eliminate air bubbles in the slurry and avoid problems in the subsequent coating process.
3. A lithium ion battery comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals; the surface of the current collector of the negative plate is coated with the lithium ion battery negative electrode material.
The active material layer coated on the current collector of the positive plate can be, but is not limited to, an active material of a chemical formula such as LiaNixCoyMzO2-bNb(wherein a is more than or equal to 0.95 and less than or equal to 1.2, x>0, y is more than or equal to 0, z is more than or equal to 0, and x + y + z is 1,0 is more than or equal to b and less than or equal to 1, M is selected from one or more of Mn and Al, N is selected from one or more of F, P and S), and the positive electrode active material can also be selected from one or more of LiCoO (lithium LiCoO), but not limited to2、LiNiO2、LiVO2、LiCrO2、LiMn2O4、LiCoMnO4、Li2NiMn3O8、LiNi0.5Mn1.5O4、LiCoPO4、LiMnPO4、LiFePO4、LiNiPO4、LiCoFSO4、CuS2、FeS2、MoS2、NiS、TiS2And the like. The positive electrode active material may be further modified, and the method of modifying the positive electrode active material is known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, and the like, and the material used in the modification may be one or a combination of more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, and the like. And the positive electrode current collector is generally a structure or a part for collecting current, and the positive electrode current collector may be any material suitable for being used as a positive electrode current collector of a lithium ion battery in the field, for example, the positive electrode current collector may include, but is not limited to, a metal foil and the like, and more specifically, may include, but is not limited to, an aluminum foil and the like.
The negative electrode current collector is generally a structure or part that collects current, and may be any of various materials suitable for use as a negative electrode current collector of a lithium ion battery in the art, for example, the negative electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a copper foil, and the like.
And the separator may be various materials suitable for lithium ion battery separators in the art, and for example, may be one or a combination of more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, and the like, including but not limited thereto.
The lithium ion battery also comprises electrolyte, and the electrolyte comprises an organic solvent, electrolyte lithium salt and an additive. Wherein the electrolyte lithium salt may be LiPF used in a high-temperature electrolyte6And/or LiBOB; or LiBF used in low-temperature electrolyte4、LiBOB、LiPF6At least one of; or LiBF used in anti-overcharge electrolyte4、LiBOB、LiPF6At least one of, LiTFSI; may also be LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2At least one of (1). And the organic solvent may be a cyclic carbonate including PC, EC; or chain carbonates including DFC, DMC, or EMC; and also carboxylic acid esters including MF, MA, EA, MP, etc. And the additives include, but are not limited to, at least one of film forming additives, conductive additives, flame retardant additives, overcharge prevention additives, additives for controlling the H2O and HF content in the electrolyte, additives for improving low temperature performance, and multifunctional additives.
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
A lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive plate and the negative plate at intervals; the negative electrode material of the lithium ion battery is coated on the negative plate.
(1) Preparation of positive plate
NCM811 positive active substance, conductive agent superconducting carbon and carbon tube, adhesive polyvinylidene fluoride according to mass ratio of 96: 2.0: 0.5: 1.5, uniformly mixing to prepare positive electrode slurry, coating the positive electrode slurry on one surface of a current collector aluminum foil, drying and rolling at 85 ℃, coating and drying the positive electrode slurry on the other surface of the aluminum foil according to the method, and then carrying out cold pressing treatment on a pole piece of the prepared aluminum foil, wherein the two surfaces of the pole piece are coated with positive electrode active material layers; and (4) trimming, cutting into pieces, slitting, and slitting to obtain the lithium ion battery positive plate.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 40 parts of active substance, 0.5 part of conductive agent, 2 parts of impregnating compound, 1.5 parts of binder, 10 parts of deionized water and 0.5 part of thickening agent.
Preferably, the active substance is one or more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composites, lithium titanate carbon composites, silicon carbon or silicon oxygen materials.
The conductive agent is conductive carbon black.
The binder is styrene butadiene rubber, and the solid content of the binder is 20%.
The impregnating compound is an IV main group oxide, the pore diameter of the impregnating compound is 100nm, and the solid content is 10%.
The thickening agent is lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
Preferably, the stirring rate in the step (A) is 200 r/min; the stirring speed in the step (B) is 500r/min, and the stirring temperature is 20 ℃; in the step (C), the stirring speed is 200r/min, and the stirring temperature is 20 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.08 mpa.
A negative pole piece, coat the above-mentioned lithium battery negative pole material on the copper foil of the mass flow body and after oven drying and coiling under 85 duC, carry on coating and drying of positive pole slurry according to the above-mentioned method on another side of copper foil, then coat the pole piece of the negative pole active material layer on the two sides of copper foil prepared with cold pressing; and cutting edges, cutting pieces, slitting, and slitting to obtain the lithium ion battery negative plate.
(3) A diaphragm: a polyethylene porous film with a thickness of 7 μm was selected as the separator.
(4) Preparing an electrolyte:
mixing lithium hexafluorophosphate (LiPF)6) Dissolving in a mixed solvent of dimethyl carbonate (DEC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) (the mass ratio of the three is 3: 5: 2) and obtaining the electrolyte.
(5) Preparing a battery:
and winding the positive plate, the diaphragm and the negative plate into a battery cell, wherein the battery cell capacity is about 5 Ah. The diaphragm is positioned between the adjacent positive plate and negative plate, the positive electrode is led out by aluminum tab spot welding, and the negative electrode is led out by nickel tab spot welding; then the electric core is placed in an aluminum-plastic packaging bag, the electrolyte is injected after baking, and finally the polymer lithium ion battery is prepared after the processes of packaging, formation, capacity grading and the like.
Example 2
Different from example 1, the preparation of the lithium ion battery negative electrode material.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 30 parts of active substance, 0.01 part of conductive agent, 0.01 part of wetting agent, 1.0 part of binder, 5 parts of deionized water and 0.1 part of thickening agent.
The active substance is a mixture of artificial graphite and hard carbon according to a mass ratio of 2: 3.
The conductive agent is a mixture of conductive carbon black and carbon nanotubes in a mass ratio of 1: 5.
The binder is styrene butadiene rubber, and the solid content of the binder is 20%.
The size is III main group oxide, the pore diameter of the size is 20nm, and the solid content is 15%.
The thickening agent is sodium carboxymethylcellulose, and the solid content of the thickening agent is 2%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
The stirring speed in the step (A) is 200 r/min; the stirring speed in the step (B) is 300r/min, and the stirring temperature is 30 ℃; in the step (C), the stirring speed is 100r/min, and the stirring temperature is 20 ℃.
The vacuum degree of the vacuumizing is-0.08 mpa.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
Different from example 1, the preparation of the lithium ion battery negative electrode material.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 30 parts of active substance, 0.1 part of conductive agent, 0.1 part of impregnating compound, 1.2 parts of binder, 0.1 part of deionized water and 0.5 part of thickening agent.
The active substance is a mixture of natural graphite and silicon carbon according to a mass ratio of 1: 4.
The conductive agent is a carbon nanotube.
The binder is styrene butadiene rubber, and the solid content of the binder is 10%.
The impregnating compound is an IV main group oxide, the pore diameter of the impregnating compound is 50nm, and the solid content is 5%.
The thickening agent is one or a mixture of two of lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
The stirring speed in the step (A) is 200 r/min; the stirring speed in the step (B) is 200r/min, and the stirring temperature is 20 ℃; in the step (C), the stirring speed is 200r/min, and the stirring temperature is 30 ℃.
The vacuum degree of the vacuumizing is-0.08 mpa.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
Different from example 1, the preparation of the lithium ion battery negative electrode material.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 35 parts of active substance, 1.2 parts of conductive agent, 1.2 parts of impregnating compound, 1.2 parts of binder, 3 parts of deionized water and 1.0 part of thickening agent.
The active substance is a mixture of artificial graphite and silicon carbon according to a mass ratio of 1: 7.
The conductive agent is a mixture of conductive carbon black and carbon fiber according to a mass ratio of 2: 1.
Preferably, the binder is a mixture of styrene butadiene rubber and polyacrylic acid in a mass ratio of 1:1, and the solid content of the binder is 20%.
Preferably, the impregnating compound is an IV main group oxide, the pore diameter of the impregnating compound is 100nm, and the solid content is 20%.
Preferably, the thickener is lithium carboxymethyl cellulose, and the solid content of the thickener is 2%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
Preferably, the stirring rate in the step (A) is 200 r/min; the stirring speed in the step (B) is 300r/min, and the stirring temperature is 25 ℃; in the step (C), the stirring speed is 250r/min, and the stirring temperature is 28 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.1 mpa.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
Different from example 1, the preparation of the lithium ion battery negative electrode material.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 45 parts of active substance, 1.5 parts of conductive agent, 0.8 part of impregnating compound, 2.2 parts of binder, 8 parts of deionized water and 0.8 part of thickening agent.
The active substance is mesocarbon microbeads.
The conductive agent is carbon fiber.
Preferably, the binder is styrene-acrylic, and the solid content of the binder is 10%.
Preferably, the impregnating compound is an IV main group oxide, the pore diameter of the impregnating compound is 90nm, and the solid content is 15%.
Preferably, the thickener is lithium carboxymethyl cellulose, and the solid content of the thickener is 2%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
Preferably, the stirring rate in the step (A) is 200 r/min; the stirring speed in the step (B) is 400r/min, and the stirring temperature is 24 ℃; in the step (C), the stirring speed is 260r/min, and the stirring temperature is 22 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.09 mpa.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
Different from example 1, the preparation of the lithium ion battery negative electrode material.
(2) Preparation method of negative electrode material
The lithium ion battery cathode material comprises the following raw materials in parts by weight: 50 parts of active substance, 1.5 parts of conductive agent, 2 parts of impregnating compound, 2.5 parts of binder, 5 parts of deionized water and 1.0 part of thickening agent.
The active substance is a mixture of hard carbon and silicon carbon according to the mass ratio of 1: 2.
The conductive agent is a mixture of conductive carbon black and graphene according to a mass ratio of 2: 1.
The binder is styrene butadiene rubber, and the solid content of the binder is 30%.
The impregnating compound is an IV main group oxide, the pore diameter of the impregnating compound is 100nm, and the solid content is 10%.
The thickening agent is lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1%.
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
Preferably, the stirring rate in the step (A) is 200 r/min; the stirring speed in the step (B) is 300r/min, and the stirring temperature is 30 ℃; in the step (C), the stirring speed is 200r/min, and the stirring temperature is 20 ℃.
Preferably, the vacuum degree of the vacuum pumping is-0.08 mpa.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from the embodiment 1 is that: the cathode material comprises the following raw materials in parts by weight: 40 parts of active substance, 0.5 part of conductive agent, 1.5 parts of binder, 5 parts of deionized water and 0.5 part of thickening agent.
The rest is the same as embodiment 1, and the description is omitted here.
Performance testing
1. The batteries prepared in the above examples 1-6 and comparative example 1 were charged and discharged at a rate of 0.7C for 300 cycles at-10 ℃, and then disassembled to observe and record the condition of the negative electrode sheet;
2. the batteries prepared in the above examples 1 to 6 and comparative example 1 were charged and discharged at a rate of 1C for 300 cycles in an ambient temperature environment, and then disassembled to observe and record the condition of the negative electrode sheet.
The test results are reported in table 1 below.
TABLE 1
Figure BDA0003076340620000131
As can be seen from the table 1, the unique pore structure of the negative electrode material prepared by the preparation method of the invention is beneficial to the infiltration of the electrolyte and the transmission of lithium ions due to the addition of the impregnating compound, so that the low-temperature lithium precipitation phenomenon and the cycle interface black spot condition are improved. As can be seen from fig. 1 and 2, the negative electrode material of comparative example 1, in which no wetting agent is used, has a large amount of lithium deposition and black spot area, and thus, it is very likely to reduce active lithium in the electrolyte, which results in a reduction in battery life, and when the deposition of lithium or black spots is severe, the safety of the battery is reduced, and the ignition performance is increased. After the slurry prepared in the embodiments 1-6 of the invention is used for the battery, the lithium precipitation condition and the black spot area are greatly reduced, and the safety performance of the battery is improved.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. A lithium ion battery negative electrode material is characterized in that: the composite material comprises the following raw materials in parts by weight: 30-50 parts of active substance, 0.01-1.5 parts of conductive agent, 0.01-2 parts of wetting agent, 1.0-2.5 parts of binder, 0.1-10 parts of deionized water and 0.1-1.0 part of thickening agent.
2. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the lithium ion battery cathode material comprises the following raw materials in parts by weight: 40-50 parts of active substance, 0.1-1.5 parts of conductive agent, 0.1-2 parts of wetting agent, 1.5-2.5 parts of binder, 0.2-6 parts of deionized water and 0.2-0.5 part of thickening agent.
3. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the active substance is one or a mixture of more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composite materials, lithium titanate carbon composite materials, silicon carbon or silicon oxygen materials.
4. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the conductive agent is one or a mixture of more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
5. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the binder is one or a mixture of more of styrene butadiene rubber, styrene-acrylic, carboxymethyl cellulose, polyacrylic acid and polytetrafluoroethylene, and the solid content of the binder is 6-40%.
6. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the size is an oxide of a third main group or a fourth main group, the aperture of the size is 10-100 nm, and the solid content is 5-20%.
7. The negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the thickening agent is one or a mixture of sodium carboxymethyl cellulose and lithium carboxymethyl cellulose, and the solid content of the thickening agent is 1-2%.
8. The preparation method of the negative electrode material of the lithium ion battery according to claim 1 or 2, characterized by comprising the following steps: comprises the following steps:
step (A): adding the conductive agent in parts by weight into a stirrer, stirring, adding the active substance in parts by weight, mixing and stirring, scraping glue, adding part of the thickening agent, stirring, scraping glue, adding part of deionized water, mixing and stirring to prepare first mixed slurry;
step (B): adding the binder, the rest of the thickening agent and the rest of the deionized water in parts by weight into the first mixed slurry, stirring and mixing, and vacuumizing to prepare second mixed slurry;
step (C): and adding the impregnating compound in parts by weight into the second mixed slurry, and stirring to obtain the lithium ion battery cathode material.
9. The preparation method of the lithium ion battery anode material according to claim 8, characterized in that: the stirring speed in the step (A) is 100-500 r/min; in the step (B), the stirring speed is 200-600 r/min, and the stirring temperature is 20-30 ℃; in the step (C), the stirring speed is 100-300 r/min, and the stirring temperature is 20-30 ℃.
10. The preparation method of the lithium ion battery anode material according to claim 8, characterized in that: the vacuum degree of the vacuum pumping is-0.08 mpa to-0.1 mpa.
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