CN111293280A - Negative plate and preparation method thereof, lithium ion battery and manufacturing method thereof - Google Patents
Negative plate and preparation method thereof, lithium ion battery and manufacturing method thereof Download PDFInfo
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- CN111293280A CN111293280A CN201811502058.0A CN201811502058A CN111293280A CN 111293280 A CN111293280 A CN 111293280A CN 201811502058 A CN201811502058 A CN 201811502058A CN 111293280 A CN111293280 A CN 111293280A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000003292 glue Substances 0.000 claims abstract description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 22
- 239000013543 active substance Substances 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000010405 anode material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
Abstract
The invention discloses a negative plate and a preparation method thereof, and a lithium ion battery and a manufacturing method thereof. The preparation method of the negative plate comprises the steps of stirring the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water in a ball milling mode to mix the materials to form slurry; coating on a substrate using the slurry; drying the coated base material to form a pole piece raw material; processing the pole piece raw material to form a negative pole piece; wherein the active substance: the styrene butadiene rubber: the conductive carbon black: the mass ratio of the CMC is (90-98): (1-3): (1-2): (0.5-2). The invention can give full play to the electrochemical performance of the material; by adopting the ball milling and stirring process, the prepared slurry is more uniform, the coating processing of the slurry is facilitated, the performance of the prepared lithium ion battery is more stable, and the gram capacity and the cycle performance of the prepared half battery can be improved.
Description
Technical Field
The invention relates to the technical field of energy storage devices, in particular to a negative plate and a preparation method thereof, a lithium ion battery and a manufacturing method thereof.
Background
With the development of the current demand for batteries, the lithium ion battery is the best novel power supply developed in the last decade, and has the characteristics of high voltage, high energy density, excellent cycle performance and the like, so that the development of electric vehicles is rapidly promoted, and the great demand of the society on the lithium ion battery is promoted.
In the prior art, graphite and silicon-carbon materials of a lithium ion battery cathode have higher specific capacity, but when the lithium ion battery prepared by adopting the oil-based binder represents electrochemical performance, the capacity is lower, the cycle performance is poorer, the attenuation is faster, and in the preparation process, the time for stirring slurry is longer.
Disclosure of Invention
In view of this, the invention provides a negative electrode sheet and a preparation method thereof, a lithium ion battery and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a negative plate, which comprises the following steps:
stirring the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water in a ball milling mode to mix the materials to form slurry;
coating on a substrate using the slurry;
drying the coated base material to form a pole piece raw material;
processing the pole piece raw material to form a negative pole piece;
wherein the active substance: the styrene butadiene rubber: the conductive carbon black: the mass ratio of the CMC is (90-98): (1-3): (1-2): (0.5-2).
Optionally, the active substance: the styrene butadiene rubber: the conductive carbon black: the mass ratio of the CMC is 96: 1: 1: 1.
optionally, the content of the solid part in the slurry is 45-55%;
preferably, the content of the solid fraction in the slurry is 50%.
Optionally, the rotation speed of the ball milling mode is 200-400 r/min;
preferably, the rotating speed is 350 r/min.
Optionally, the stirring time of the ball milling mode is 10-20 minutes;
preferably, the stirring time is 15 minutes.
Optionally, the concentration of the CMC glue solution is 1-2%;
preferably, the concentration of the CMC glue solution is 1 percent.
Optionally, the mixing the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber, and the deionized water by ball milling to form a slurry further includes:
preparing the CMC glue solution;
adding zirconium balls with different diameters into a ball milling tank with a polytetrafluoroethylene lining;
and placing the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water in the ball milling tank for ball milling.
Optionally, the specific steps of adding zirconium balls with different diameters into the ball milling tank with the polytetrafluoroethylene lining are as follows: adding 1-10 zirconium balls with the diameter of 5mm and 5-50 zirconium balls with the diameter of 10mm into the ball milling tank;
preferably, 6 zirconium balls with the diameter of 5mm and 30 zirconium balls with the diameter of 10mm are added into the ball milling tank.
Optionally, drying the coated substrate specifically includes:
placing the coated base material in a blast drying oven, and drying at the temperature of 30-60 ℃ for 1-3 hours;
and (3) placing the base material in a vacuum drying oven, and drying for 1-3 hours at the temperature of 100-130 ℃.
Optionally, drying the coated substrate specifically includes:
placing the coated base material in an air-blast drying oven, and drying at the temperature of 40 ℃ for 2 hours;
the substrate was placed in a vacuum oven and dried at 120 ℃ for 2 hours.
A second aspect of the present invention provides a method of manufacturing a lithium ion battery, including:
preparing a negative plate by the preparation method of any one of the above;
and assembling the negative pole pieces to form the lithium ion battery.
The third aspect of the invention provides a negative electrode sheet prepared by the preparation method of any one of the above.
A fourth aspect of the invention provides a lithium ion battery comprising the negative electrode sheet as described above.
According to the preparation method of the negative plate, the electrochemical performance of the material can be more fully exerted by changing the proportion of the active substance to the aqueous binder; by adopting the ball milling and stirring process, the prepared slurry is more uniform, the coating processing of the slurry is facilitated, the performance of the prepared lithium ion battery is more stable, and the efficiency of preparing the half battery can be improved.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings, in which:
fig. 1 is a graph showing a comparison of gram capacity test results of an anode material prepared by the method for preparing an anode material provided by the present invention using graphite as an active material and an anode material prepared using an oil system;
fig. 2 is a graph showing a comparison of cycle performance test results of the negative electrode material prepared by the method for preparing the negative electrode material according to the present invention using graphite as an active material and the negative electrode material prepared using an oil system;
fig. 3 is a graph showing a gram capacity test result of an anode material prepared by the method for preparing an anode material according to the present invention using silicon carbon as an active material, compared with an anode material prepared using an oil system;
fig. 4 is a graph showing a comparison of cycle performance test results of the anode material prepared by the method for preparing the anode material according to the present invention using silicon carbon as an active material and the anode material prepared using an oil system.
Detailed Description
The present invention will be described below based on examples, but the present invention is not limited to only these examples. In the following detailed description of the present invention, certain specific details are set forth in order to avoid obscuring the nature of the present invention, well-known methods, procedures, and components have not been described in detail.
Further, those of ordinary skill in the art will appreciate that the drawings provided herein are for illustrative purposes and are not necessarily drawn to scale.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, what is meant is "including, but not limited to".
In the description of the present invention, it is to be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
The application provides a preparation method of a negative plate, which comprises the following steps:
s1: stirring CMC glue solution, active substances, conductive carbon black, styrene butadiene rubber and deionized water in a ball milling mode, adding the CMC glue solution, the active substances, the conductive carbon black, the styrene butadiene rubber and the deionized water into a ball milling tank, and then placing the ball milling tank on a planetary ball mill for stirring, so that the materials are mixed to form slurry;
s2: coating the substrate with the slurry formed by mixing;
s3: drying the coated base material to form a pole piece raw material;
s4: processing the raw material of the negative plate, such as cutting and other processes, to form the negative plate;
wherein, the active substance: styrene-butadiene rubber: conductive carbon black: the mass ratio of CMC (namely sodium carboxymethyl cellulose) is (90-98): (1-3): (1-2): (0.5-2), such as (90-98), can be 90, 91, 93, 96, 98, etc.; in (1-3), the number may be 1, 2, 3, etc.; in (1-2), 1, 1.5, 2, etc. may be used; among (0.5 to 2), 0.5, 1, 1.5, 2, etc. may be mentioned.
By adopting the preparation method of the negative plate, the electrochemical performance of the material can be more fully exerted by changing the proportion of the active substance and the aqueous binder; through adopting ball-milling stirring technology for the thick liquids of preparation are more even, are favorable to the thick liquids to carry out coating processing, make the lithium ion battery performance of preparation more stable, and the ball-milling mode can shorten the churning time, improves the efficiency of preparing half-cell.
Specifically, the active material may be selected from one or a mixture of two of graphite and silicon carbon. Preferably, the active substance: styrene-butadiene rubber: conductive carbon black: the mass ratio of CMC is 96: 1: 1: 1, so as to better exert the electrochemical performance of the material.
The content of the solid part in the S1 slurry is preferably 45% to 55%, such as 45%, 43%, 50%, 52%, 55%, etc., and preferably, the content of the solid part in the slurry is 50% to improve the electrochemical performance of the anode material.
The rotation speed of the ball milling mode in the step S1 is 200-400 r/min, such as 200r/min, 250r/min, 300r/min, 350r/min, 400r/min and the like, preferably 350r/min, so that the uniformity of the slurry is improved, and the quality of subsequent coating is improved.
The stirring time of the ball milling method may be 10 to 20 minutes, such as 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, and the like, and preferably, the stirring time is 15 minutes, so as to further improve the uniformity of the slurry.
The concentration of the CMC glue solution selected in S1 is 1% to 2%, such as 1%, 1.3%, 1.5%, 1.8%, 2%, and the like, and preferably, the concentration of the CMC glue solution is 1% to increase the strength and the adhesiveness of the negative electrode sheet.
It can be understood that, the S1 stirs the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber, and the deionized water by means of ball milling, and before mixing the above materials to form the slurry, the method further includes:
s01: preparing the CMC glue solution;
s02: adding zirconium balls with different diameters into a ball milling tank with a polytetrafluoroethylene lining, wherein the volume of the ball milling tank can be 100-200 ml, 100mi, 120ml, 150ml, 180ml and 200ml, and the volume can be specifically selected according to the amount of each mixed material;
at this time, in S1, the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber, and the deionized water are added into a ball milling tank for ball milling and mixing.
It should be noted that, the above-mentioned S01 and S02 have no sequence, and any step may be executed first.
Wherein, S02 is added with zirconium balls with different diameters in a ball milling tank with a polytetrafluoroethylene lining, which is specifically as follows: adding 1-10 zirconium balls with the diameter of 5mm and 5-50 zirconium balls with the diameter of 10mm into a ball milling tank, for example, adding 1, 2, 5, 6, 8 and 10 zirconium balls with the diameter of 5mm, adding 5, 10, 15, 20, 25, 30, 35, 45, 50 zirconium balls with the diameter of 10mm, and the like, preferably adding 6 zirconium balls with the diameter of 5mm and 30 zirconium balls with the diameter of 10mm into the ball milling tank to increase the sufficient stirring of the materials. In practice, the diameter and number of the zirconium balls may be selected as required, and are not limited to the above values.
And S3, drying the coated substrate, specifically:
s31: placing the coated base material in a blast drying oven, and drying at the temperature of 30-60 ℃ for 1-3 hours, wherein the temperature can be selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃ and the like, and the drying time can be 1 hour, 2 hours, 3 hours and the like;
s32: and placing the base material in a vacuum drying oven, and drying at the temperature of 100-130 ℃ for 1-3 hours, wherein the drying temperature can be 100 ℃, 110 ℃, 120 ℃, 125 ℃, 130 ℃ and the like, and the drying time can be 1 hour, 2 hours, 3 hours and the like.
By adopting the step drying mode, the coated base material can be fully dried, the adhesion effect of active substances on the base material is ensured, and the phenomena of cracking and stripping of the base material are prevented.
Preferably, the coated substrate is dried at a temperature of 40 ℃ for 2 hours while being placed in an air drying oven in S31; in S32, the substrate is dried at 120 ℃ for 2 hours while being placed in a vacuum oven. By performing the drying step by step at the above temperature, the adhesion effect of the slurry after coating and the drying of the base material can be further improved.
The invention also provides a manufacturing method of the lithium ion battery, which is characterized by comprising the following steps:
preparing a negative plate by the preparation method of any one of the above embodiments;
and assembling the negative pole pieces to form the lithium ion battery.
Obviously, the lithium ion battery manufactured by the method has higher cycle performance and slower attenuation because the negative plate is prepared by the method described in the above embodiment.
In addition, the invention also provides a negative electrode sheet prepared by the preparation method of the negative electrode sheet in any embodiment. Meanwhile, the invention also provides a lithium ion battery which comprises the negative plate.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
A preparation method of a negative plate comprises the following steps:
step 1): preparing CMC glue solution with the concentration of 1 percent;
step 2): adding 6 zirconium balls with the diameter of 5mm and 30 zirconium balls with the diameter of 10mm into a ball milling tank with the inner lining of polytetrafluoroethylene (100-200 ml);
step 3): sequentially adding CMC glue solution, silicon carbon, conductive carbon black (Super-P), Styrene Butadiene Rubber (SBR) and deionized water into a ball milling tank, wherein the mass ratio of the substances is as follows: SBR: Super-P: the CMC glue solution is 96: 1: 1: 1, forming a solid-liquid mixture. Wherein, the solid-liquid mixture (namely the slurry formed after stirring) has the solid part content of 50 percent;
step 4): placing the ball milling tank on a planetary ball mill for stirring, wherein the rotating speed is 350r/min, and the stirring time is 15 min;
step 5): coating the base material by using the stirred slurry;
step 6): drying the coated base material, placing the base material in an air-blast drying oven to dry for 2 hours at 40 ℃, and then transferring the base material to a vacuum drying oven to dry for 2 hours at 120 ℃;
step 7): and cutting the pole piece into a proper size by using a slicing machine to form the required negative pole piece.
Example 2
Different from the embodiment 1, the silicon carbon in the step 3) is changed into graphite.
Comparative example 1
Different from the embodiment 1, the silicon carbon, the conductive carbon black (Super-P) and the oily binder are sequentially added into the ball milling tank in the step 3), namely the CMC glue solution and the Styrene Butadiene Rubber (SBR) are replaced by the oily binder.
Comparative example 2
Different from the embodiment 1, graphite, conductive carbon black (Super-P) and an oily binder are sequentially added into the ball milling tank in the step 3), namely CMC glue solution and Styrene Butadiene Rubber (SBR) are replaced by the oily binder.
The comparison graphs obtained by testing the negative electrode sheets prepared in the above examples 1-2 and comparative examples 1-2 are shown in fig. 1-4, and it can be seen from the graphs that the electrochemical performance of the negative electrode material can be more fully exerted by adopting the proper proportion of the active material and the aqueous binder in the invention, and the gram capacity and the charge-discharge cycle performance of the negative electrode sheet prepared by the method are obviously improved compared with those of the negative electrode sheet prepared by the oily binder, and obviously, the electrochemical performance of the negative electrode sheet prepared by the method of the invention is better.
Those skilled in the art will readily appreciate that the above-described preferred embodiments may be freely combined, superimposed, without conflict.
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.
Claims (13)
1. A preparation method of a negative plate is characterized by comprising the following steps:
stirring the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water in a ball milling mode to mix the materials to form slurry;
coating on a substrate using the slurry;
drying the coated base material to form a pole piece raw material;
processing the pole piece raw material to form a negative pole piece;
wherein the active substance: the styrene butadiene rubber: the conductive carbon black: the mass ratio of the CMC is (90-98): (1-3): (1-2): (0.5-2).
2. The method of manufacturing according to claim 1, wherein the active substance: the styrene butadiene rubber: the conductive carbon black: the mass ratio of the CMC is 96: 1: 1: 1.
3. the method of claim 1, wherein the content of the solid portion in the slurry is 45% to 55%;
preferably, the content of the solid fraction in the slurry is 50%.
4. The preparation method according to claim 1, wherein the rotation speed of the ball milling mode is 200-400 r/min;
preferably, the rotating speed is 350 r/min.
5. The preparation method according to claim 1, wherein the stirring time of the ball milling method is 10 to 20 minutes;
preferably, the stirring time is 15 minutes.
6. The preparation method according to claim 1, wherein the concentration of the CMC glue solution is 1-2%;
preferably, the concentration of the CMC glue solution is 1 percent.
7. The preparation method of claim 1, wherein the stirring of the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water by the ball milling method further comprises the following steps before mixing the materials to form the slurry:
preparing the CMC glue solution;
adding zirconium balls with different diameters into a ball milling tank with a polytetrafluoroethylene lining;
and placing the CMC glue solution, the active substance, the conductive carbon black, the styrene butadiene rubber and the deionized water in the ball milling tank for ball milling.
8. The preparation method of claim 7, wherein the adding of the zirconium balls with different diameters into the ball milling tank with the polytetrafluoroethylene lining is specifically as follows: adding 1-10 zirconium balls with the diameter of 5mm and 5-50 zirconium balls with the diameter of 10mm into the ball milling tank;
preferably, 6 zirconium balls with the diameter of 5mm and 30 zirconium balls with the diameter of 10mm are added into the ball milling tank.
9. The method according to claim 1, wherein the drying of the coated substrate is carried out by:
placing the coated base material in a blast drying oven, and drying at the temperature of 30-60 ℃ for 1-3 hours;
and (3) placing the base material in a vacuum drying oven, and drying for 1-3 hours at the temperature of 100-130 ℃.
10. The method according to claim 9, wherein the drying of the coated substrate is carried out by:
placing the coated base material in an air-blast drying oven, and drying at the temperature of 40 ℃ for 2 hours;
the substrate was placed in a vacuum oven and dried at 120 ℃ for 2 hours.
11. A method of manufacturing a lithium ion battery, comprising:
preparing a negative electrode sheet by the preparation method according to any one of claims 1 to 10;
and assembling the negative pole pieces to form the lithium ion battery.
12. A negative electrode sheet, characterized by being produced by the production method according to any one of claims 1 to 10.
13. A lithium ion battery comprising the negative electrode sheet according to claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811502058.0A CN111293280A (en) | 2018-12-10 | 2018-12-10 | Negative plate and preparation method thereof, lithium ion battery and manufacturing method thereof |
Applications Claiming Priority (1)
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Application publication date: 20200616 |