CN111525131A - Negative electrode material for lithium ion battery and preparation method thereof - Google Patents

Negative electrode material for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN111525131A
CN111525131A CN202010268178.XA CN202010268178A CN111525131A CN 111525131 A CN111525131 A CN 111525131A CN 202010268178 A CN202010268178 A CN 202010268178A CN 111525131 A CN111525131 A CN 111525131A
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short
graphite
negative electrode
cmc
deionized water
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吕新坡
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Chongqing Zijian Electronic Co ltd
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Chongqing Zijian Electronic Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a negative electrode ingredient of a lithium ion battery, which is formed by mixing graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), N-methyl pyrrolidone (NMP) and deionized water, wherein the infiltration of graphite and water is improved by adding a mixture of water and NMP in the negative electrode ingredient process, so that the graphite is more uniformly and stably dispersed in slurry, the surface tension of the slurry is reduced, the fluidity of the slurry is better, the processing performance is better, particularly in the coating process, the coating amount of the head and the tail of a pole piece is easier to control, the quality of the pole piece is improved, the difficulty of the coating operation of the negative electrode ingredient is reduced, the coating qualification rate is improved, and the full-automatic production operation of products is facilitated.

Description

Negative electrode material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to a negative electrode ingredient of a lithium ion battery, in particular to a negative electrode ingredient of a lithium ion battery and a preparation method thereof.
Background
Currently, lithium ion batteries are widely used. The anode is mostly nickel, cobalt and manganese system, and the cathode is graphite system.
The cathode comprises the following ingredients: graphite, deionized water, CMC (sodium carboxymethylcellulose), SP (conductive carbon black), SBR (styrene butadiene rubber). The material mixing process comprises the following steps: mixing CMC with water to prepare glue solution, adding SP to prepare conductive glue solution, adding graphite, stirring uniformly, adding SBR, and stirring uniformly.
The pole piece coating of the digital battery cell is to adopt a transfer type or extrusion type coating machine to uniformly coat a section of positive and negative pole materials on an aluminum foil or a copper foil, a section of empty foil area is arranged between coating materials, the length of the coated pole piece is required to be stable, and the coating amount is required to be uniform.
The surface tension of the conventional negative electrode ingredient is large, so that the coating amount of the negative electrode slurry at the head and the tail of a pole piece is often large, and the coating amount of the head and the tail of the pole piece is adjusted by adjusting the action time of a coating valve and a reflux valve of an extrusion coating machine; the transfer coater adjusts the coating amount by adjusting the roll speed ratio of the head part and the tail part, and although the equipment is adjusted, the coating amount of the head part and the tail part of the pole piece is also influenced by a slurry system, viscosity and the like, so that the technical problems of frequent equipment adjustment, long adjustment time and unsatisfactory adjustment effect are caused.
And once more lead to thick partially in pole piece head and tail coating volume, it also can cause bad influence to back process and electric core performance, is the roll-in process after the coating, and this process is through two rolls from top to bottom, adds certain pressure, presses the pole piece to technology thickness, and head afterbody thick partially can cause this position excessive pressure, falls the material, bad phenomenon such as inefficacy.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a negative electrode ingredient of a lithium ion battery and a preparation method thereof, wherein the negative electrode ingredient has the advantages of small surface tension, better fluidity, convenience in preparation, easier control of coating amount, reduction of coating process difficulty and contribution to full-automatic production operation of products.
In order to achieve the purpose, the invention provides a negative electrode ingredient of a lithium ion battery, which is formed by mixing graphite, conductive carbon black (SP for short), sodium carboxymethylcellulose (CMC for short), styrene butadiene rubber (SBR for short), N-methyl pyrrolidone (NMP for short) and deionized water, wherein the weight ratio of the ingredients is as follows: 95:1.5-2:1.5-2:1.2-1.8:1.4-1.8:110-130.
Preferably, the weight ratio of the graphite, the conductive carbon black (SP for short), the sodium carboxymethylcellulose (CMC for short), the styrene butadiene rubber (SBR for short), the N-methylpyrrolidone (NMP for short) and the deionized water is as follows: 95:1.7:1.7:1.5:1.6:120.
Compared with the prior art, the negative electrode material for the lithium ion battery provided by the invention has the beneficial effects that:
the mixture of water and NMP is added in the negative pole batching process, so that the infiltration of graphite and water is improved, the graphite is more uniformly and stably dispersed in the slurry, the surface tension of the slurry is reduced, the fluidity of the slurry is better, the processing performance is better, particularly in the coating process, the coating amount of the head and the tail of the pole piece is easier to control, the quality of the pole piece is improved, the difficulty of the negative pole batching coating operation is reduced, the coating qualified rate is improved, and the full-automatic production operation of products is facilitated.
In order to achieve the above object, the present invention further provides a preparation method of a negative electrode material for a lithium ion battery, comprising the following steps:
s1, mixing sodium carboxymethylcellulose (CMC) and deionized water according to the weight ratio of 1.5:95-105, and stirring for a certain time to obtain a glue solution;
s2, adding conductive carbon black (SP for short) into the glue solution obtained in the step S1, and stirring for a certain time, wherein the mass ratio of the conductive carbon black (SP for short) to the sodium carboxymethyl cellulose (CMC for short) is 0.75-1.4;
s3, continuing to add graphite and stirring for a certain time to obtain slurry, wherein the weight ratio of the graphite to the sodium carboxymethyl cellulose (CMC for short) is 95: 1.5-2;
s4, preparing standing water: weighing deionized water with the weight of 1.2-1.8% of the weight of graphite, weighing N-methylpyrrolidone (NMP for short) with the same weight as the deionized water, mixing the deionized water and the N-methylpyrrolidone (NMP for short), and standing for a period of time;
s5, adding the standing water in the step S4 into the slurry in the step S3, and stirring for a certain time;
and S6, continuing to add styrene butadiene rubber (SBR for short) and stirring for a certain time, wherein the weight ratio of the graphite to the styrene butadiene rubber (SBR for short) is 95: 1.2-1.8.
Preferably, in step S1, sodium carboxymethylcellulose (CMC) and deionized water are mixed in a ratio of 1.5: 98.5.
Preferably, the viscosity of the glue solution in the step S1 is 8000-12000 mpa.s.
Preferably, the mass ratio of the conductive carbon black (abbreviated as SP) to the sodium carboxymethyl cellulose (abbreviated as CMC) in step S2 is 1.
Preferably, the weight ratio of the graphite to the sodium carboxymethyl cellulose (CMC for short) in step S3 is 95: 1.7.
Preferably, in step S4, the deionized water and N-methylpyrrolidone (NMP for short) are mixed and then left for two hours or more.
Preferably, the styrene-butadiene rubber (SBR for short) described in step S6 is a 50% concentration SBR aqueous solution.
Preferably, the weight ratio of the graphite to the styrene butadiene rubber (abbreviated as SBR) in the step S6 is 95: 1.5.
Compared with the prior art, the preparation method of the cathode material of the lithium ion battery has the beneficial effects that:
the negative electrode ingredient produced by the method has the advantage of small surface tension, so that the slurry has better fluidity and better processing performance, particularly in an extrusion coating process, the coating amount of the head and the tail of the pole piece is easier to control, the quality of the pole piece is improved, the difficulty of the coating operation of the negative electrode ingredient is reduced, and the coating qualification rate is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram of the mechanism of hydrolysis of NMP provided by the present invention;
FIG. 2 is a schematic diagram of the combination of NMP and deionized water provided by the present invention;
FIG. 3 is a schematic representation of the combination of NMP and graphite provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a negative electrode ingredient of a lithium ion battery, which is formed by mixing graphite, conductive carbon black (SP for short), sodium carboxymethylcellulose (CMC for short), styrene butadiene rubber (SBR for short), N-methyl pyrrolidone (NMP for short) and deionized water, wherein the weight ratio of the ingredients is as follows: 95:1.5-2:1.5-2:1.2-1.8:1.4-1.8:110-130.
Specifically, the weight ratio of graphite, conductive carbon black (SP for short), sodium carboxymethylcellulose (CMC for short), styrene butadiene rubber (SBR for short), N-methylpyrrolidone (NMP for short) and deionized water is as follows: 95:1.7:1.7:1.5:1.6:120.
The mixture of water and NMP is added in the negative pole batching process, so that the infiltration of graphite and water is improved, the graphite is more uniformly and stably dispersed in the slurry, the surface tension of the slurry is reduced, the fluidity of the slurry is better, the processing performance is better, particularly in the coating process, the coating amount of the head and the tail of the pole piece is easier to control, the quality of the pole piece is improved, the difficulty of the negative pole batching coating operation is reduced, the coating qualified rate is improved, and the full-automatic production operation of products is facilitated.
Example two
The invention also provides a preparation method of the cathode material of the lithium ion battery, which comprises the following steps:
firstly, preparing glue solution: mixing sodium carboxymethylcellulose (CMC for short) and deionized water at a ratio of 1.5:98.5 for 1.5h, wherein the viscosity is controlled within the range of 8000-12000 mpa.s;
secondly, adding conductive carbon black (SP) with the same weight as the sodium carboxymethylcellulose (CMC) into the glue solution, and stirring for 1.5 h;
thirdly, adding graphite, and stirring for 3 hours to form slurry, wherein the weight ratio of the graphite to the sodium carboxymethyl cellulose (CMC for short) is 95: 1.7;
fourthly, preparing standing water: weighing deionized water accounting for 1.5 percent of the total weight of the graphite by using a stainless steel basin, adding N-methylpyrrolidone (NMP for short) with the same weight as the deionized water, and standing for 2 hours;
fifthly, adding the mixture of NMP and deionized water which has the standing time of more than 2 hours into the slurry, and stirring for 0.5 hour;
sixthly, adding styrene butadiene rubber (SBR for short) and stirring for 0.5h, wherein the SBR is SBR aqueous solution with the concentration of 50 percent.
FIG. 1 shows the mechanism of hydrolysis of NMP, which is inhibited by the addition of small amounts of deionized water, primarily because deionized water and NMP, when mixed, form hydrogen bonds with NMP.
As shown in fig. 2, NMP releases a large amount of heat during the formation of hydrogen bonds, which require much energy to be broken, so that generally, a solution of NMP and water is more difficult to volatilize because more energy is required for volatilization.
The negative electrode graphite is originally not hydrophilic, the infiltration of the graphite and water can be improved by adding a small amount of NMP, so that the negative electrode graphite and the binder are better mixed, the coating quality of a pole piece is finally improved, after the NMP is added, the NMP and the water form hydrogen bonds, the NMP and the graphite are easily combined as shown in a figure 3, the contact angle and the surface tension of the graphite in the water are reduced, the wettability of the graphite and the water is increased, the graphite is more easily dispersed into the water, the difficulty of coating operation of the negative electrode ingredients is reduced, and the coating qualification rate is improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The negative electrode ingredient of the lithium ion battery is characterized by being formed by mixing graphite, conductive carbon black (SP for short), sodium carboxymethylcellulose (CMC for short), styrene butadiene rubber (SBR for short), N-methyl pyrrolidone (NMP for short) and deionized water, wherein the weight ratio of the ingredients is as follows: 95:1.5-2:1.5-2:1.2-1.8:1.4-1.8:110-130.
2. The negative electrode material of the lithium ion battery according to claim 1, wherein the weight ratio of the graphite, the conductive carbon black (SP), the sodium carboxymethyl cellulose (CMC), the Styrene Butadiene Rubber (SBR), the N-methyl pyrrolidone (NMP) and the deionized water is as follows: 95:1.7:1.7:1.5:1.6:120.
3. A preparation method of a negative electrode material of a lithium ion battery is characterized by comprising the following steps:
s1, mixing sodium carboxymethylcellulose (CMC) and deionized water according to the weight ratio of 1.5:95-105, and stirring for a certain time to obtain a glue solution;
s2, adding conductive carbon black (SP for short) into the glue solution obtained in the step S1, and stirring for a certain time, wherein the mass ratio of the conductive carbon black (SP for short) to the sodium carboxymethyl cellulose (CMC for short) is 0.75-1.4;
s3, continuing to add graphite and stirring for a certain time to obtain slurry, wherein the weight ratio of the graphite to the sodium carboxymethyl cellulose (CMC for short) is 95: 1.5-2;
s4, preparing standing water: weighing deionized water with the weight of 1.2-1.8% of the weight of graphite, weighing N-methylpyrrolidone (NMP for short) with the same weight as the deionized water, mixing the deionized water and the N-methylpyrrolidone (NMP for short), and standing for a period of time;
s5, adding the standing water in the step S4 into the slurry in the step S3, and stirring for a certain time;
and S6, continuing to add styrene butadiene rubber (SBR for short) and stirring for a certain time, wherein the weight ratio of the graphite to the styrene butadiene rubber (SBR for short) is 95: 1.2-1.8.
4. The method of claim 3, wherein in step S1, the sodium carboxymethylcellulose (CMC) and the deionized water are mixed in a ratio of 1.5: 98.5.
5. The method as claimed in claim 3, wherein the viscosity of the glue solution in step S1 is 8000-12000 mpa.s.
6. The method according to claim 3, wherein the mass ratio of the conductive carbon black (SP) to the sodium carboxymethyl cellulose (CMC) in step S2 is 1.
7. The method according to claim 3, wherein the weight ratio of the graphite to the sodium carboxymethyl cellulose (CMC) in step S3 is 95: 1.7.
8. The method for preparing the negative electrode material of the lithium ion battery according to claim 3, wherein the deionized water and the N-methylpyrrolidone (NMP for short) are mixed in step S4 and then are allowed to stand for more than two hours.
9. The method of claim 3, wherein the styrene-butadiene rubber (SBR for short) in step S6 is a 50% SBR aqueous solution.
10. The method for preparing the negative electrode material of the lithium ion battery according to claim 3, wherein the weight ratio of the graphite to the styrene-butadiene rubber (SBR for short) in the step S6 is 95: 1.5.
CN202010268178.XA 2020-04-08 2020-04-08 Negative electrode material for lithium ion battery and preparation method thereof Withdrawn CN111525131A (en)

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CN113363589A (en) * 2021-05-19 2021-09-07 东莞维科电池有限公司 Lithium ion battery and preparation method thereof

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