CN114725370A - Water-based positive electrode slurry and preparation method thereof - Google Patents
Water-based positive electrode slurry and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 51
- 239000003292 glue Substances 0.000 claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 26
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- 239000000853 adhesive Substances 0.000 claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229920005553 polystyrene-acrylate Polymers 0.000 claims abstract description 15
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- 239000006256 anode slurry Substances 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002562 thickening agent Substances 0.000 claims abstract description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 239000006257 cathode slurry Substances 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 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 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011591 potassium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 18
- 238000004880 explosion Methods 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- HCSCWJCZRCSQFA-UHFFFAOYSA-N 1-methylpyrrolidin-2-one;hydrate Chemical compound O.CN1CCCC1=O HCSCWJCZRCSQFA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005518 electrochemistry Effects 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
An aqueous positive electrode slurry and a preparation method thereof comprise the following steps: mixing 0.1-3.0% of polystyrene-acrylate LB300 aqueous adhesive, 0.5-2.5% of aqueous thickening agent and part of deionized water according to mass percentage, firstly stirring at low speed, and then stirring at high speed to form first glue solution; adding 0.1-2.0% of conductive agent into the first glue solution, and stirring at high speed to form a second glue solution; adding 97.1% of lithium ion battery anode material adopting lithium cobaltate into the second glue solution, and stirring at low speed to obtain a third glue solution; adding deionized water into the third glue solution according to 100-150% of the mass of the lithium cobaltate lithium ion battery anode material for viscosity regulation, stirring the slurry at a low speed, and vacuumizing; and (4) defoaming the slurry obtained in the step (4), directly charging air to discharge vacuum, and slowly stirring the slurry to obtain the aqueous anode slurry. The process can effectively reduce the production cost, has no pollution to the atmosphere, and effectively ensures the health and safety of production personnel.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of electrochemistry, in particular to aqueous anode slurry and a preparation method thereof.
[ background ] A method for producing a semiconductor device
Compared with lead-acid batteries, nickel-metal hydride batteries and nickel-cadmium batteries, lithium ion batteries have the advantages of higher energy density, small self-discharge, long cycle life and the like, and are widely applied to the fields of consumer electronics and power batteries at present. The preparation of lithium ion batteries requires auxiliary material binders, which are also important factors affecting the battery composition and its overall performance.
Currently, the anode slurry for lithium ion battery, especially the anode plate for lithium ion battery produced by electronic cigarette manufacturers, is generally produced by using a fluoropolymer such as PVDF (polyvinylidene fluoride) as an adhesive, using a strongly polar organic compound such as NMP (dimethyl pyrrolidone), dimethyl phthalein amine, dimethyl sulfoxide and the like as a solvent for PVDF, using acetone as a diluent, and using an oil slurry stirring system. However, the coating smoothness of the anode slurry of the organic system is low, the drying difficulty of the pole piece is high, the equipment investment is large, and the following defects exist: firstly, the organic solvent NMP has larger usage amount, and simultaneously the price of the NMP is expensive and the usage cost is high; secondly, the NMP water absorption of the oily slurry is strong, the requirements on the environmental humidity in the slurry stirring and coating processes are high, and the cost of accessory facilities is high; thirdly, the slurry is coated on the pole piece, waste gas is generated in the drying process, the pollution to the ecological environment is large, the influence on the body health of production operators is large, toxic gas pollutes the environment and is difficult to recover, and the like. Causing environmental pollution and harm to human body.
There is an urgent need to develop a new positive electrode binder for avoiding environmental pollution and reducing production costs caused by the use of oily slurry.
[ summary of the invention ]
The embodiment of the invention provides water-based anode slurry and a preparation method thereof, wherein PVDF is replaced by a water-based binder, NMP is replaced by deionized water to prepare the anode water-based slurry, the pollution problem generated in the preparation process of the anode oily slurry is solved, and the cycle, the multiplying power and the safety performance of a lithium ion battery prepared by using the slurry meet the commercial requirements.
In order to achieve the purpose, the technical scheme is as follows:
in a first aspect, a method for preparing an aqueous positive electrode slurry according to an embodiment of the present invention includes the steps of:
(1) mixing 0.1-3.0% of polystyrene-acrylate LB300 aqueous adhesive, 0.5-2.5% of aqueous thickening agent and part of deionized water according to mass percentage, firstly stirring at low speed for 5-10min, and then stirring at high speed for 30-50min to form first glue solution;
(2) adding 0.1-2.0% of conductive agent by mass percent into the first glue solution, and stirring at high speed for 30-50min to form a second glue solution;
(3) adding 97.1% of lithium cobaltate lithium ion battery anode material into the second glue solution by mass percent, and stirring at low speed for 30-50min to obtain a third glue solution;
(4) adding deionized water into the third glue solution according to 100-150% of the mass of the lithium cobaltate lithium ion battery positive electrode material by mass percent to adjust the viscosity, controlling the solid content (namely the solid powder accounts for the specific gravity of the slurry) to be 71-75%, stirring the slurry at a low speed for 20-30min, then vacuumizing, controlling the vacuum degree to be-0.08-0.09 MPa, controlling the fineness of the slurry to be 75-80um and the viscosity of the slurry to be 4500-8000 MPa · s;
(5) and (5) defoaming the slurry obtained in the step (4), directly charging air to discharge vacuum, and slowly stirring the slurry to obtain the water-based anode slurry.
Further, the low-speed rotation speed in the step (1) is as follows: revolution is 5-25r/min, and rotation is 0-200 r/min; the high-speed rotating speed is as follows: the conversion rate is 10-30r/min, and the conversion rate is 200-250 r/min.
Further, the low-speed rotation speed in the step (2) is as follows: the revolution is 10-30r/min, and the rotation is 1000-1500 r/min.
Further, the rotation speed of the low-speed stirring in the step (3) is as follows: the revolution is 5-20r/min, and the rotation is 100-150 r/min.
Further, the rotation speed of the low-speed stirring in the step (4) is as follows: the revolution is 5-20r/min, and the rotation is 100-150 r/min.
Further, the aqueous thickener is at least one of lithium carboxymethyl cellulose, sodium carboxymethyl cellulose (CMC) and potassium carboxymethyl cellulose.
Further, the conductive agent is at least one of graphene, conductive carbon black, conductive graphite and carbon nanotubes.
Further, the deionized water added in the step (4) is deionized water with the conductivity of less than 2 mu s/cm.
In a second aspect, the invention provides an aqueous cathode slurry according to an embodiment, and the aqueous cathode slurry prepared by the method.
One or more technical solutions provided in the embodiments of the present invention have at least the following technical effects or advantages:
the positive electrode material adopted by the lithium ion battery adopts the polystyrene-acrylate LB300 as the water-based adhesive, so that the strong adhesive force between the negative electrode material for the lithium ion battery and the current collector is kept, the mechanical property of a pole piece is improved, the water-based adhesive is used for replacing PVDF in the prior art, and the deionized water is used for replacing positive electrode water-based slurry prepared by NMP, so that the pollution problem generated in the preparation process of the positive electrode oil-based slurry is solved, the health and safety of production personnel are effectively ensured, and the multiplying power, the circulation and the safety of the lithium ion battery are improved.
Moreover, the anode aqueous slurry prepared by the process has low requirement on the environmental humidity, the stirring difficulty is reduced, the vacuum is unloaded after the slurry is stirred and vacuumized without using protective gases such as hydrogen, nitrogen and the like, and air is directly filled for vacuum unloading, so that the requirement on stirring equipment is reduced, and the production cost is reduced; and the water-based anode lithium ion battery uses deionized water as a solvent, water vapor is evaporated during coating and drying, the air is not polluted, decontamination equipment is not needed, the equipment cost is further reduced, the water-based anode lithium ion battery is safe and reliable in production and use processes, health threats to production personnel are avoided, the evaporation and drying temperature of water is lower than that of an organic solvent, the coating and drying temperature is reduced, the energy consumption is reduced, the requirement on coating equipment is also reduced, and the environment-friendly production of the lithium ion battery is realized.
[ description of the drawings ]
Fig. 1 shows a 100-cycle performance test of a lithium ion battery provided by the present invention.
Fig. 2 is a rate performance test curve of the lithium ion battery provided by the invention.
[ detailed description ] embodiments
The present invention will be further described with reference to the following specific examples.
Example one
The preparation method of the aqueous positive electrode slurry of the embodiment includes the following steps:
(1) mixing 0.1% of polystyrene-acrylate LB300 aqueous adhesive, 1.5% of sodium carboxymethyl cellulose CMC and part of deionized water according to mass percentage, firstly stirring at low speed for 5min, wherein the rotating speed is as follows: the revolution rate is 10r/min, and the revolution rate is 50 r/min; then, stirring at high speed for 30min, wherein the rotating speed is as follows: the revolution speed is 10r/min, and the revolution speed is 200r/min, so as to form a first glue solution;
(2) adding 1% of conductive agent by mass into the first glue solution, and stirring at high speed for 30min at the rotating speed of: the revolution is 10r/min, the autorotation is 1000r/min, and a second glue solution is formed, wherein the conductive agent in the embodiment is conductive graphite;
(3) adding 97.1% of lithium cobaltate lithium ion battery anode material into the second glue solution by mass percent, stirring at low speed for 30min, wherein the rotating speed is as follows: the revolution is 5r/min, and the autorotation is 100r/min to obtain a third glue solution;
(4) adding deionized water into the third glue solution according to 100% of the mass of the lithium cobaltate lithium ion battery positive electrode material by mass percentage for adjusting viscosity, wherein the deionized water is deionized water with the conductivity less than 2 mu s/cm, the solid content (namely the proportion of solid powder in the slurry) is controlled to be 71%, stirring the slurry at a low speed for 20min, and then vacuumizing at the rotating speed of: the revolution is 5r/min while stirring, the autorotation is 100r/min, the vacuum degree is-0.08 MPa, and the fineness of the slurry is controlled to be 75 um;
(5) and (5) defoaming the slurry obtained in the step (4), directly charging air to discharge vacuum, and slowly stirring the slurry to obtain the water-based anode slurry.
Example two
The preparation method of the aqueous positive electrode slurry of the embodiment includes the following steps:
(1) mixing 2% of polystyrene-acrylate LB300 aqueous adhesive, 2% of sodium carboxymethyl cellulose CMC and part of deionized water according to mass percentage, firstly stirring at low speed for 10min, wherein the rotating speed is as follows: the revolution is 15r/min, and the autorotation is 150 r/min; then, stirring at high speed for 50min, wherein the rotating speed is as follows: revolution is 25r/min, autorotation is 220r/min, and first glue solution is formed;
(2) adding 2% of conductive agent in the first glue solution by mass percentage, and stirring at a high speed for 50min at the rotating speed of: the revolution is 25r/min, the autorotation is 1200r/min, a second glue solution is formed, and the conductive agent in the embodiment is conductive graphite;
(3) adding 97.1% of lithium cobaltate lithium ion battery anode material into the second glue solution by mass percent, stirring at low speed for 50min, wherein the rotating speed is as follows: the revolution is 15r/min, and the autorotation is 125r/min, so as to obtain a third glue solution;
(4) adding deionized water into the third glue solution according to 100-150% of the mass of the lithium cobaltate lithium ion battery anode material by mass percent for adjusting viscosity, wherein the deionized water is deionized water with the conductivity less than 2 mu s/cm, the solid content (namely the proportion of solid powder in the slurry) is controlled to be 72%, stirring the slurry at a low speed for 25min, and then vacuumizing at the rotating speed of: during stirring, the revolution is 15r/min, the rotation is 120r/min, the vacuum degree is-0.09 MPa, and the fineness of the slurry is controlled to be 76 um;
(5) and (5) defoaming the slurry obtained in the step (4), directly filling air for vacuum relief, and slowly stirring the slurry to obtain the water-based anode slurry.
EXAMPLE III
The method for preparing an aqueous positive electrode slurry of this embodiment includes the steps of:
(1) mixing 3% of polystyrene-acrylate LB300 aqueous adhesive, 2.5% of sodium carboxymethyl cellulose CMC and part of deionized water according to mass percentage, firstly stirring at low speed for 10min, wherein the rotating speed is as follows: the revolution speed is 25r/min, and the revolution speed is 200 r/min; then, stirring at high speed for 50min, wherein the rotating speed is as follows: the revolution is 30r/min, the rotation is 250r/min, and a first glue solution is formed;
(2) adding 2.0% of conductive agent in the first glue solution by mass percent, and stirring at a high speed for 50min at the rotating speed of: revolution is 30r/min, autorotation is 1500r/min, a second glue solution is formed, and the conductive agent in the embodiment is conductive graphite;
(3) adding 97.1% of lithium cobaltate lithium ion battery anode material into the second glue solution by mass percent, stirring at low speed for 50min, wherein the rotating speed is as follows: revolution is 20r/min, autorotation is 150r/min, and third glue solution is obtained;
(4) adding deionized water into the third glue solution according to the mass percentage of 150% of the mass of the lithium cobaltate lithium ion battery anode material for adjusting viscosity, wherein the deionized water is the deionized water with the conductivity less than 2 mu s/cm, the solid content (namely the proportion of the solid powder in the slurry) is controlled to be 75%, stirring the slurry at a low speed for 30min, and then vacuumizing at the rotating speed of: during stirring, the revolution is 20r/min, the rotation is 150r/min, the vacuum degree is-0.09 MPa, and the fineness of the slurry is controlled to be 80 um;
(5) and (5) defoaming the slurry obtained in the step (4), directly charging air to discharge vacuum, and slowly stirring the slurry to obtain the water-based anode slurry.
Comparative example 1
A preparation method of oily cathode slurry comprises the following steps:
(1) mixing 0.1% of polyvinylidene fluoride (PVDF) oily adhesive, 0.3% of conductive agent and 97.1% of lithium cobaltate lithium ion battery positive electrode material according to mass percent, stirring dry powder, firstly stirring at low speed for 5min, and rotating speed is as follows: the revolution rate is 10r/min, and the revolution rate is 50 r/min; then, stirring at high speed for 30min, wherein the rotating speed is as follows: the revolution speed is 10r/min, and the revolution speed is 200r/min, so as to form a first glue solution; the conductive agent in this comparative example was conductive graphite;
(2) adding 1.23% of conductive slurry into the first glue solution by mass percent for muddy stirring, and stirring at a low speed for 10min at the rotating speed of: the revolution is 25r/min, the rotation is 0r/min, and a second glue solution is formed, wherein the conductive slurry in the embodiment is carbon nano tube CNTs;
(3) adding 26.16 percent of oily solvent NMP into the second glue solution according to the mass percentage, stirring at a high speed for 50min, wherein the rotating speed is as follows: the revolution is 30r/min, the autorotation is 1500r/min, and a third glue solution is obtained:
(4) adding an oily solvent NMP (N-methyl pyrrolidone) into the third glue solution by mass percent, wherein the mass of the oily solvent NMP accounts for 1.5 percent of that of the lithium cobaltate lithium ion battery anode material, the viscosity is regulated, the solid content (namely the proportion of solid powder in the slurry) is controlled to be 71 percent, the slurry is stirred at a low speed for 30min and then is vacuumized, and the rotating speed is as follows: stirring at revolution speed of 5r/min, autorotation speed of 100r/min, vacuum degree of-0.08 MPa, and slurry fineness of 75-80 um;
(5) and (4) defoaming the slurry obtained in the step (4), filling hydrogen and nitrogen protective gas for vacuum unloading, and slowly stirring the slurry to obtain the oily anode slurry.
In the above three embodiments, in the step (1), the polystyrene-acrylate LB300 and the comparative example one in the prior art are added with the polyvinylidene fluoride PVDF in an equal mass percentage (the content of the polyvinylidene fluoride PVDF added in the comparative example two and the comparative example three are different and are not described here again), the pole piece bonding effect and the capacity retention rate of the cycle of 100 cycles are tested, and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the low addition ratio of the two binders results in poor binding effect, because the addition amount of the binders is small, and the active substances and the binders on the pole pieces are not uniformly dispersed and locked. When the proportion of the added adhesive is 2% and 3%, the peel strength of the pole piece is good, and the capacity retention rates of the two adhesives after 100 cycles are basically similar. However, the polystyrene-acrylate LB300 is adopted as the aqueous adhesive, has lower toxicity than polyvinylidene fluoride PVDF, is economic and environment-friendly, solves the pollution problem generated in the preparation process of the positive electrode oily slurry, and the positive electrode aqueous slurry prepared by the process has low requirement on the environmental humidity and reduced stirring difficulty, and the vacuum is unloaded after the slurry is stirred and vacuumized without using protective gases such as hydrogen, nitrogen and the like, and is directly filled with air for vacuum unloading, so that the requirement on stirring equipment is reduced, and the production cost is reduced; and secondly, the water-based anode lithium ion battery takes deionized water as a solvent, and water vapor is evaporated during coating and drying, so that the water-based anode lithium ion battery has no pollution to the atmosphere, does not need decontamination equipment, further reduces the equipment cost, is safe and reliable in production and use processes, and does not cause health threat to production personnel.
The invention adopts a water-based adhesive polystyrene-acrylate LB300 to replace the original positive electrode oily adhesive PVDF, and the water-based solvent deionized water replaces the oily solvent NMP. Optimizing the production process and improving the production process. Compared with the existing lithium ion battery prepared by using the oily binder, the lithium ion battery prepared by using the aqueous binder has the advantages that the cycle, the multiplying power and the safety performance meet the requirements.
As can be seen from the peel strength of the pole pieces with different adhesives and the analysis in Table 1, the pole pieces prepared by respectively adding 2% of polystyrene-acrylate LB300 in the second example and 2% of polyvinylidene fluoride PVDF in the second comparative example are better.
Therefore, the batteries prepared by adding 2% of the polystyrene-acrylate LB300 of the second example and the polyvinylidene fluoride PVDF of the comparative example are respectively marked as 1 and 2, and the electrochemical performance test and the safety test are carried out, and the results are shown in Table 2.
TABLE 2
| Kind of battery | Security testing project | quantity/PCS | Description of test | Security determination | |
| 1 | Normal temperature external |
3 | Without ignition and explosion | OK | |
| 1 | High temperature external |
3 | Without ignition and explosion | OK | |
| 1 | Overcharge and overdischarge | 6 | Without ignition and explosion | OK | |
| 1 | Impact of |
3 | Without ignition and explosion | OK | |
| 1 | |
3 | Without ignition and explosion | OK | |
| 1 | |
3 | Without ignition and explosion | OK | |
| 1 | High temperature storage (65 ℃, 7 days) | 3 | Without ignition and explosion | OK | |
| 2 | Normal temperature external |
3 | Without ignition and explosion | OK | |
| 2 | High temperature external |
3 | Fire and | NG | |
| 2 | Overcharge and overdischarge | 6 | Without ignition and explosion | OK | |
| 2 | Impact of |
3 | Without fire and explosion | OK | |
| 2 | |
3 | Without ignition and explosion | OK | |
| 2 | |
3 | Without ignition and explosion | OK | |
| 2 | High temperature storage (65 ℃, 7 days) | 3 | Without ignition and explosion | OK |
As can be seen from table 2, the safety performance of the battery prepared from the aqueous binder, polystyrene-acrylate LB300, was better than that of the battery prepared from the oily binder, PVDF.
And the batteries prepared according to the pole pieces of the second embodiment and the second embodiment are subjected to 100-cycle life test, and as can be seen from a cycle life curve chart of fig. 1, the battery prepared from the water-based binder polystyrene-acrylate LB300 has the same cycle performance as the battery prepared from the oil-based binder PVDF, but the battery prepared from the water-based binder polystyrene-acrylate LB300 has higher discharge capacity and good specific capacity per unit volume.
Meanwhile, the rate capability test of the lithium ion battery is carried out according to the battery prepared from the two-pole piece of the embodiment, the test result is shown as a curve shown in fig. 2, and the rate of the lithium ion battery prepared from the aqueous binder completely meets the design requirement.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, except for the cases listed in the specific embodiments; all equivalent variations of the methods and principles of the present invention are intended to be within the scope of the present invention.
Claims (9)
1. The preparation method of the aqueous positive electrode slurry is characterized by comprising the following steps of:
(1) mixing 0.1-3.0% of polystyrene-acrylate LB300 aqueous adhesive, 0.5-2.5% of aqueous thickening agent and part of deionized water according to mass percentage, firstly stirring at low speed for 5-10min, and then stirring at high speed for 30-50min to form first glue solution;
(2) adding 0.1-2.0% of conductive agent by mass percent into the first glue solution, and stirring at high speed for 30-50min to form a second glue solution;
(3) adding 97.1% of lithium cobaltate lithium ion battery anode material into the second glue solution by mass percent, and stirring at low speed for 30-50min to obtain a third glue solution;
(4) adding deionized water into the third glue solution according to 100-150% of the mass of the lithium cobaltate lithium ion battery positive electrode material by mass percent to adjust the viscosity, controlling the solid content to be 71-75%, stirring the slurry at low speed for 20-30min, then vacuumizing, controlling the vacuum degree to be-0.08-0.09 MPa, controlling the fineness of the slurry to be 75-80um and the viscosity of the slurry to be 4500-8000 MPa · s;
(5) and (5) defoaming the slurry obtained in the step (4), directly charging air to discharge vacuum, and slowly stirring the slurry to obtain the water-based anode slurry.
2. The method for preparing an aqueous cathode slurry according to claim 1, wherein the low speed rotation speed in step (1) is: revolution is 5-25r/min, and rotation is 0-200 r/min; the high-speed rotating speed is as follows: the conversion rate is 10-30r/min, and the conversion rate is 200-250 r/min.
3. The method for preparing an aqueous cathode slurry according to claim 1, wherein the low speed in step (2) is: the revolution is 10-30r/min, and the rotation is 1000-1500 r/min.
4. The method for preparing an aqueous cathode slurry according to claim 1, wherein the rotation speed of the low-speed stirring in the step (3) is as follows: the revolution is 5-20r/min, and the rotation is 100-150 r/min.
5. The method for preparing an aqueous cathode slurry according to claim 1, wherein the rotation speed of the low-speed stirring in the step (4) is as follows: the revolution is 5-20r/min, and the rotation is 100-150 r/min.
6. The method for preparing an aqueous cathode slurry according to claim 1, wherein the aqueous thickener is at least one of lithium carboxymethyl cellulose, sodium carboxymethyl cellulose (CMC) and potassium carboxymethyl cellulose.
7. The method for preparing an aqueous cathode slurry according to claim 1, wherein the conductive agent is at least one of graphene, conductive carbon black, conductive graphite and carbon nanotubes.
8. The method as claimed in claim 1, wherein the deionized water added in step (4) has a conductivity of < 2 μ s/cm.
9. An aqueous positive electrode slurry characterized in that: an aqueous positive electrode slurry prepared by the method according to any one of claims 1 to 8.
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| WO2017190366A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Secondary battery and preparation method therefor |
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| CN112768638A (en) * | 2021-01-15 | 2021-05-07 | 厦门海辰新能源科技有限公司 | Water-based positive electrode slurry and preparation method thereof |
| CN113675532A (en) * | 2021-08-13 | 2021-11-19 | 东莞维科电池有限公司 | Diaphragm and preparation method and application thereof |
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