CN111769287B - Aqueous adhesive for battery, application of aqueous adhesive, lithium ion battery positive electrode material, lithium ion battery positive electrode sheet and lithium ion battery - Google Patents
Aqueous adhesive for battery, application of aqueous adhesive, lithium ion battery positive electrode material, lithium ion battery positive electrode sheet and lithium ion battery Download PDFInfo
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- CN111769287B CN111769287B CN202010701142.6A CN202010701142A CN111769287B CN 111769287 B CN111769287 B CN 111769287B CN 202010701142 A CN202010701142 A CN 202010701142A CN 111769287 B CN111769287 B CN 111769287B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
- 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
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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 provides an aqueous binder for a battery, application thereof, a lithium ion battery anode material, a lithium ion battery anode sheet and a lithium ion battery, and relates to the technical field of battery materials, wherein the aqueous binder for the battery comprises an acrylonitrile copolymer and a tetrafluoroethylene copolymer, and the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 1: (0.1-0.5), and the acrylonitrile copolymer and the tetrafluoroethylene copolymer are water-soluble polymers, so that the problems of brittleness and easy breakage of the conventional aqueous positive plate are solved. The aqueous adhesive for the battery provided by the invention is soft in property and good in processing performance, improves the mechanical performance of a pole piece, ensures the electrical performance of a lithium ion battery, and effectively reduces environmental pollution and eliminates the health hidden trouble of operators by taking water as a solvent.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to an aqueous binder for a battery, application of the aqueous binder, a lithium ion battery positive electrode material, a lithium ion battery positive electrode sheet and a lithium ion battery.
Background
Since the mass production of lithium ion batteries in the nineties of the last century, lithium ion batteries have been widely used in various fields due to their advantages of high volumetric energy ratio, high weight energy ratio, high voltage, low discharge rate, no memory effect, long cycle life, and the like.
The conventional lithium ion battery positive electrode material adopts polyvinylidene fluoride as an adhesive, an organic solvent is required to be adopted for dissolving and then coating on a current collector, and the organic solvent is easy to volatilize, so that not only can environmental pollution be caused, but also the health of operating personnel can be influenced.
In recent years, some research organizations try to adopt water-soluble polyacrylic acid as a battery adhesive, but the single polyacrylic acid adhesive is brittle and hard and is easy to break, and the mechanical performance of a pole piece is influenced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a water-based adhesive for a battery, which is used for relieving the technical problems of hard and brittle property and easy breakage of a pole piece when polyacrylic acid is used as the adhesive for the battery.
The second object of the present invention is to provide an application of the above-mentioned aqueous binder for batteries.
The invention also provides a lithium ion battery positive electrode material comprising the aqueous binder for batteries.
The fourth object of the present invention is to provide a positive electrode sheet for a lithium ion battery, which comprises the above aqueous binder for a battery or the above positive electrode material for a lithium ion battery.
The fifth object of the present invention is to provide a lithium ion battery comprising the aqueous binder for battery, the positive electrode material for lithium ion battery, or the positive electrode sheet for lithium ion battery.
The aqueous binder for the battery comprises an acrylonitrile copolymer and a tetrafluoroethylene copolymer, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 1: (0.1-0.5), and both the acrylonitrile copolymer and the tetrafluoroethylene copolymer are water-soluble copolymers.
Further, the acrylonitrile copolymer comprises at least one of LA132, LA133 and LA138, preferably LA 138;
further, the tetrafluoroethylene copolymer comprises at least one of Dupont 30LX, INOFLON 9300 and Feiteng TY-P40, and preferably Feiteng TY-P40.
Further, the binder for the battery further comprises at least one of carboxymethyl cellulose, chitosan derivatives, sodium alginate, styrene butadiene rubber, polyvinylidene fluoride, hydroxypropyl methyl cellulose and methyl cellulose.
The invention provides application of the aqueous binder for the battery in a lithium ion battery anode material or a lithium ion battery cathode material.
The invention provides a lithium ion battery cathode material which comprises the aqueous binder for batteries.
Further, the lithium ion battery positive electrode material further comprises an organic acid, preferably, the organic acid comprises at least one of fulvic acid, citric acid and acetic acid.
Further, the mass ratio of the organic acid in the lithium ion battery anode material is 0.1-5%, and preferably 0.2-0.5%.
Further, the lithium ion battery positive electrode material also comprises a positive electrode active substance and a conductive agent;
preferably, the positive active material includes at least one of lithium nickelate, lithium manganate, lithium cobaltate, lithium manganese phosphate, lithium iron phosphate, lithium vanadium phosphate, lithium nickel cobalt aluminum oxide, and lithium nickel cobalt manganese oxide;
preferably, the conductive agent includes at least one of acetylene black, carbon nanotubes, graphite, carbon black, graphene, and carbon fibers.
The invention also provides a lithium ion battery positive plate which comprises the aqueous binder for the battery or the lithium ion battery positive material.
The invention also provides a lithium ion battery, which comprises the aqueous binder for the battery, the positive electrode material for the lithium ion battery or the positive electrode sheet for the lithium ion battery.
The aqueous adhesive for the battery provided by the invention adopts the mutual cooperation of polyacrylonitrile and polytetrafluoroethylene in a specific mass ratio, maintains excellent bonding performance, increases the flexibility and toughness, improves the mechanical performance of a pole piece, avoids the problems of easy generation of floating powder, winding and breaking of the pole piece and the like during pole piece slitting, ensures the electrical performance of a lithium ion battery, and effectively reduces the environmental pollution and eliminates the health hidden danger of operating personnel by using water as a solvent.
The positive electrode material for the lithium ion battery provided by the invention adopts the aqueous binder for the battery as the binder, so that the strong adhesive force between the positive electrode material for the lithium ion battery and a current collector is maintained, the mechanical property of a pole piece is improved, the electrical property of the lithium ion battery is ensured, cheap and easily available water can be used as a solvent, the environmental pollution is effectively reduced, and the health hidden danger of operators is eliminated.
The lithium ion battery positive plate provided by the invention adopts the aqueous adhesive for the battery as the adhesive, so that the strong adhesive force between the positive material for the lithium ion battery and the current collector is maintained, the mechanical property of the plate is improved, the electrical property of the lithium ion battery is ensured, the hidden danger of environmental pollution and human health influence caused by adopting an organic solvent is eliminated, and the lithium ion battery positive plate has a wider application prospect.
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 described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a charge-discharge performance test curve of a lithium ion battery provided in embodiment 1 of the present invention;
fig. 2 is a charge/discharge performance test curve of the lithium ion battery provided in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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.
According to one aspect of the invention, the invention provides a water-based adhesive for a battery, which comprises polyacrylonitrile and polytetrafluoroethylene, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 1: (0.1-0.5), and both the acrylonitrile copolymer and the tetrafluoroethylene copolymer are water-soluble polymers.
Typically, but not limitatively, the invention provides an aqueous binder for batteries in which the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is, for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1: 0.5.
The positive electrode material for the lithium ion battery provided by the invention adopts the aqueous binder for the battery as the binder, so that the strong adhesive force between the positive electrode material for the lithium ion battery and a current collector is maintained, the mechanical property of a pole piece is improved, cheap and easily available water can be used as a solvent, the environmental pollution is effectively reduced, and the health hidden trouble of operators is eliminated.
In a preferred embodiment of the present invention, the acrylonitrile copolymer provided by the present invention comprises at least one of LA132, LA133, LA138, preferably LA 138;
in a preferred embodiment of the present invention, the tetrafluoroethylene copolymer provided by the present invention comprises at least one of Dupont 30LX, INOFLON 9300, Feiteng TY-P40, preferably Feiteng TY-P40.
In a preferred embodiment of the present invention, the aqueous binder for batteries further comprises at least one of carboxymethyl cellulose, chitosan derivatives, sodium alginate, styrene-butadiene rubber, polyvinylidene fluoride, hydroxypropyl methyl cellulose, and methyl fiber.
The styrene butadiene rubber and the polyvinylidene fluoride are both in a water emulsion form, so that the styrene butadiene rubber and the polyvinylidene fluoride can be uniformly mixed with acrylonitrile copolymer and tetrafluoroethylene copolymer, and the obtained adhesive still uses water as a solvent, so that the adhesive is safe and environment-friendly.
The above-mentioned "at least one kind" means that the aqueous binder for batteries may further include one of carboxymethyl cellulose, chitosan derivatives, sodium alginate, styrene-butadiene rubber, polyvinylidene fluoride, hydroxypropyl methyl cellulose or methyl fiber, or a mixture of two or more of carboxymethyl cellulose, chitosan derivatives, sodium alginate, styrene-butadiene rubber, polyvinylidene fluoride, hydroxypropyl methyl cellulose or methyl fiber, in addition to the acrylonitrile copolymer and the tetrafluoroethylene copolymer.
In a preferred embodiment of the present invention, the aqueous binder for a battery may further include one or a mixture of several of carboxymethyl cellulose, chitosan derivatives, sodium alginate, styrene-butadiene rubber, polyvinylidene fluoride, hydroxypropyl methyl cellulose, or methyl fiber, depending on the type of the specific positive electrode material active material or negative electrode material active material and the type of the conductive agent, in addition to the acrylonitrile copolymer and the tetrafluoroethylene copolymer, to further improve the adhesion property of the aqueous binder to the current collector.
According to a second aspect of the invention, the invention provides the use of the above aqueous binder for batteries in a positive electrode material of a lithium ion battery or a negative electrode material of a lithium ion battery.
The aqueous binder for the battery can be used for a positive electrode material of the lithium ion battery, and can be used for adhering a positive active substance and a conductive agent in the positive electrode material of the lithium ion battery to a positive current collector, and can also be used for a negative electrode material of the lithium ion battery, and adhering a negative active substance and a conductive agent in the negative electrode material of the lithium ion battery to a negative current collector.
According to a third aspect of the invention, the invention provides a lithium ion battery cathode material, which comprises the aqueous binder for batteries.
The positive electrode material for the lithium ion battery provided by the invention adopts the aqueous binder for the battery as the binder, so that the bonding strength between the positive electrode material for the lithium ion battery and the current collector is greatly improved, the mechanical property of a pole piece is improved, cheap and easily available water can be used as a solvent, the environmental pollution is effectively reduced, and the health hidden trouble of operators is eliminated.
In a preferred embodiment of the present invention, the lithium ion battery positive electrode material further includes an organic acid.
Generally, when a positive plate of a battery is prepared, a positive material of the lithium ion battery needs to be dispersed in a solvent to prepare a positive slurry, and then the positive slurry is coated on a positive current collector, dried and rolled to obtain the positive plate of the lithium ion battery.
However, since the positive active material has strong alkalinity, the positive slurry prepared by dispersing the positive material of the lithium ion battery including the positive active material, the conductive agent and the adhesive in water is weak alkali or even strong alkalinity, while the positive current collector is generally an aluminum foil or an aluminum alloy foil, and the positive slurry which is weak alkali or even strong alkalinity is very easy to cause corrosion of the aluminum foil or the aluminum alloy foil, and damage the mechanical properties of the pole piece and the electrical properties of the battery.
According to the invention, the organic acid is added into the lithium ion battery anode material, so that the pH value of the anode slurry is adjusted through the organic acid, the pH value of the anode slurry is reduced, the anode slurry is prevented from corroding aluminum foil or aluminum alloy foil, the mechanical property of the pole piece is maintained, and the yield of the anode pole piece is improved.
In a preferred embodiment of the present invention, the organic acid comprises at least one of fulvic acid, citric acid and acetic acid.
In a preferred embodiment of the present invention, a weak acid is selected as the organic acid to facilitate the adjustment of the pH of the positive electrode slurry, wherein the pH of the slurry is preferably adjusted to 7 to 9.
The term "at least one" as used herein means that the organic acid may be any one of fulvic acid, citric acid and acetic acid, or a mixture of any two or more of fulvic acid, citric acid and acetic acid.
In a preferred embodiment of the present invention, the mass ratio of the organic acid in the lithium ion battery positive electrode material is 0.1% to 5%, preferably 0.2 to 0.5%.
Typically, but not by way of limitation, the organic acid is present in the lithium ion battery positive electrode material in an amount of, for example, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, or 5% by mass.
The mass ratio of the organic acid in the lithium ion battery anode material is controlled to be 0.1-5% so that the anode slurry is kept in a proper pH range, a current collector cannot be corroded due to an overhigh pH value, an anode active substance cannot be corroded due to an overlow pH value, especially when the mass ratio of the organic acid in the lithium ion battery anode material is 0.2-0.5%, the pH value of the anode slurry prepared from the lithium ion battery anode material is more moderate, and the prepared anode sheet has better mechanical property.
In a preferred embodiment of the present invention, the lithium ion battery positive electrode material further includes a positive electrode active material and a conductive agent.
In a further preferred embodiment of the present invention, the positive electrode active material includes at least one of lithium nickelate, lithium manganate, lithium cobaltate, lithium manganese phosphate, lithium iron phosphate, lithium vanadium phosphate, lithium nickel cobalt aluminum oxide, and lithium nickel cobalt manganese oxide.
The "at least one type" means that the positive electrode active material may be lithium nickelate, lithium manganate, lithium cobaltate, lithium manganese phosphate, lithium iron phosphate, lithium vanadium phosphate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminum oxide, or may be a mixture of any two types of the positive electrode active materials, such as a mixture of lithium cobaltate and lithium manganate, a mixture of lithium nickel oxide and lithium iron phosphate, a mixture of lithium vanadium phosphate and lithium manganese phosphate, or the like, or may be a mixture of any three types or more of the positive electrode active materials, such as a mixture of lithium cobaltate, lithium manganate and lithium nickel oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate and lithium nickel cobalt manganese oxide, or the like.
In a preferred embodiment of the present invention, the conductive agent includes at least one of acetylene black, carbon nanotubes, graphite, carbon black, graphene, and carbon fibers.
The "at least one" means that the conductive agent may be acetylene black, carbon nanotubes, graphite, carbon black, graphene or carbon fibers, or may be a mixture of any two or more of acetylene black, carbon nanotubes, graphite, carbon black, graphene or carbon fibers.
According to a fourth aspect of the invention, the invention also provides a lithium ion battery positive plate, which comprises the aqueous binder for batteries or the lithium ion battery positive material.
The lithium ion battery positive plate provided by the invention adopts the aqueous binder for the battery provided by the invention as the binder, so that the mechanical property of the positive plate is effectively improved, and the yield of the positive plate is improved.
In a preferred embodiment of the present invention, the method for preparing a positive electrode sheet of a lithium ion battery provided by the present invention comprises the steps of:
and adding the lithium ion battery anode material into water, uniformly dispersing to obtain lithium ion battery anode slurry, coating the lithium ion battery anode slurry on an anode current collector, and drying and rolling to obtain the lithium ion battery anode sheet.
According to a fifth aspect of the invention, the invention provides a lithium ion battery, which comprises the aqueous binder for batteries, the positive electrode material for lithium ion batteries or the positive electrode sheet for lithium ion batteries.
The lithium ion battery provided by the invention adopts the water-based adhesive provided by the invention to replace the original polyvinylidene chloride adhesive, the preparation process is more environment-friendly and safer, and the electrical property of the prepared lithium ion battery is equivalent to that of the lithium ion battery adopting polyvinylidene chloride as the adhesive.
The technical scheme provided by the invention is further explained by combining the embodiment and the comparative example.
The sources of the raw materials in the following examples and comparative examples are as follows: the acrylonitrile copolymer is purchased from Chengdingdele power supply technology company, and the model is LA 138; the tetrafluoroethylene copolymer is purchased from New chemical Material Co., Ltd, type TY-P401, Feiteng Asia chemical industry in Wuhan. The rest raw materials can be obtained by commercial purchase without special description.
Example 1
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.2%, acrylonitrile copolymer: 1.5%, tetrafluoroethylene copolymer: 0.5%, fulvic acid: 0.3% and acetylene black: 2.5 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 3: 1.
Example 2
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.4%, acrylonitrile copolymer: 1.8%, tetrafluoroethylene copolymer: 0.3%, fulvic acid: 0.2% and acetylene black: 2.3 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 6: 1.
Example 3
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: nickel cobalt lithium aluminate: 95.5%, acrylonitrile copolymer: 1.5%, tetrafluoroethylene copolymer: 0.5%, and acetylene black: 2.5 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 3: 1.
Example 4
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.6%, acrylonitrile copolymer: 1.8%, tetrafluoroethylene copolymer: 0.3% and acetylene black: 2.3 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 6: 1.
Example 5
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.3%, acrylonitrile copolymer: 2%, tetrafluoroethylene copolymer: 0.2%, fulvic acid: 0.2% and acetylene black: 2.3 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 10: 1.
Example 6
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.4%, acrylonitrile copolymer: 1.4%, tetrafluoroethylene copolymer: 0.7% fulvic acid: 0.2% and acetylene black: 2.3 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 2: 1.
Example 7
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.4%, acrylonitrile copolymer: 1.5%, tetrafluoroethylene copolymer: 0.5% acetic acid: 0.1% and acetylene black: 2.5 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 3: 1.
Example 8
The embodiment provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.3%, acrylonitrile copolymer: 1.5%, tetrafluoroethylene copolymer: 0.5% citric acid: 0.5% and acetylene black: 2.2 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 3: 1.
Comparative example 1
This comparative example provides a positive electrode material for a lithium ion battery, which is different from that of example 1 in that polyvinylidene fluoride is used as a binder instead of acrylonitrile copolymer and tetrafluoroethylene copolymer.
Comparative example 2
This comparative example provides a positive electrode material for a lithium ion battery, which is different from that of example 1 in that polyacrylic acid was used as a binder instead of acrylonitrile copolymer and tetrafluoroethylene copolymer.
Comparative example 3
The comparative example provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.2%, acrylonitrile copolymer: 2%, fulvic acid: 0.3% and acetylene black: 2.5 percent.
Comparative example 4
The comparative example provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.2%, tetrafluoroethylene copolymer: 2%, fulvic acid: 0.3% and acetylene black: 2.5 percent.
Comparative example 5
The comparative example provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.2%, acrylonitrile copolymer: 1.9%, tetrafluoroethylene copolymer: 0.05%, fulvic acid: 0.1% and acetylene black: 2.5 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 19: 1.
Comparative example 6
The comparative example provides a lithium ion battery cathode material, which comprises the following raw materials in parts by mass: lithium nickel cobalt manganese oxide: 95.2%, acrylonitrile copolymer: 1%, tetrafluoroethylene copolymer: 0.05%, fulvic acid: 1% and acetylene black: 2.5 percent, wherein the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 3: 1.
Examples 9 to 16
Examples 9 to 16 each provide a positive electrode sheet for a lithium ion battery, which is prepared from the positive electrode materials for lithium ion batteries provided in examples 1 to 8, respectively.
The lithium ion battery positive plate is prepared according to the following steps:
dissolving the lithium ion battery anode material in water to prepare anode slurry, then coating the anode slurry on an aluminum foil, drying and rolling to obtain the lithium ion battery anode sheet.
Comparative examples 7 to 12
Comparative examples 7 to 12 respectively provide positive electrode sheets of lithium ion batteries, which were prepared from the positive electrode materials of lithium ion batteries provided in comparative examples 1 to 6, respectively. The preparation methods of the positive electrode plates of the lithium ion batteries provided in the comparative examples 8 to 12 are the same as those in example 9, and are not described herein again.
The preparation method of the positive plate of the lithium ion battery provided in the comparative example 7 comprises the following steps: dissolving the lithium ion battery anode material in N-methyl pyrrolidone to prepare anode slurry, then coating the anode slurry on aluminum foil, drying and rolling to obtain the lithium ion battery anode sheet.
Test example 1
10000 lithium ion battery positive electrode sheets provided in examples 9 to 16 and comparative examples 7 to 12 were respectively wound to prepare lithium ion batteries, and then the yield, the first charge capacity, the first discharge capacity, and the capacity after 100 cycles of the lithium ion batteries were respectively measured, and the capacity retention rate after 100 cycles of the lithium ion batteries was calculated, and the results are shown in table 1.
During the process of preparing the lithium ion battery, the lithium ion battery positive plate which cannot be prepared is sorted out, the yield is calculated, the reason of defective products is analyzed, the hardness is too high, the mechanical property is poor, the broken sheet cannot be wound normally, or the material is seriously dropped during the winding process, so that the preparation of the battery cannot be completed.
The test conditions for the lithium ion battery to carry out the charge and discharge test are as follows: constant-current constant-voltage charging: cutoff voltage 4.2V, charging current 2400mA, cutoff current 100mA, ambient temperature: 25 ℃; constant current discharging: cut-off voltage of 3.0V, discharge current of 2400mA, ambient temperature 25 ℃.
In addition, in the lithium ion battery prepared in the test example, the negative electrode sheets are all CMC and SBR as binders, and graphite is used as an active substance; the diaphragms are all PE; the electrolyte is commercial lithium ion battery electrolyte.
TABLE 1
Remarking: the positive electrode material for the lithium ion battery provided in comparative example 4 cannot be made into a slurry, so that the positive electrode sheet for the lithium ion battery cannot be prepared, and the measurement items in comparative example 10 have no data.
Fig. 1 is a charge-discharge performance test curve of a lithium ion battery provided in embodiment 1 of the present invention; FIG. 2 is a test curve of the charge and discharge performance of the lithium ion battery provided in comparative example 1 of the present invention; as can be seen from fig. 1 and 2, the electrical property test curve of the lithium ion battery provided in example 1 is equivalent to the electrical property test curve of the lithium ion battery provided in comparative example 1, which also indicates that cheap and pollution-free water is used as a solvent instead of N-methyl pyrrolidone, and a battery aqueous binder comprising a mixture of polyacrylonitrile and styrene butadiene rubber is used as a binder of the positive electrode material of the lithium ion battery instead of polyvinylidene fluoride, and the bonding strength of the positive electrode material to aluminum foil is substantially consistent with that of vinylidene chloride, so that the prepared positive electrode sheet has excellent mechanical properties, and the electrical property of the lithium ion battery prepared by the positive electrode sheet is equivalent to that of the conventional positive electrode material of the lithium ion battery using polyvinylidene fluoride as a binder.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. The positive electrode material for the lithium ion battery is characterized by comprising an aqueous binder for the battery and an organic acid, wherein the aqueous binder for the battery is composed of an acrylonitrile copolymer and a tetrafluoroethylene copolymer, and the mass ratio of the acrylonitrile copolymer to the tetrafluoroethylene copolymer is 1: (0.1-0.5), and both the acrylonitrile copolymer and the tetrafluoroethylene copolymer are water-soluble polymers;
the mass ratio of the organic acid in the lithium ion battery anode material is 0.1-5%,
the pH value of the anode material formed by dispersing the lithium ion battery anode material in water is 7-9, and the organic acid is weak acid.
2. The positive electrode material of claim 1, wherein the acrylonitrile copolymer comprises at least one of LA132, LA133, and LA 138.
3. The positive electrode material as claimed in claim 1, wherein the acrylonitrile copolymer is LA 138.
4. The positive electrode material according to claim 1,
the tetrafluoroethylene copolymer comprises at least one of DuPont 30LX, INOFLON 9300 and Feiteng TY-P40.
5. The positive electrode material according to claim 1, wherein the tetrafluoroethylene copolymer is Feiteng TY-P40.
6. The positive electrode material for lithium ion batteries according to claim 1,
the organic acid comprises at least one of fulvic acid, citric acid and acetic acid.
7. The lithium ion battery cathode material according to claim 6, wherein the mass ratio of the organic acid in the lithium ion battery cathode material is 0.2-0.5%.
8. The lithium ion battery positive electrode material according to claim 1, further comprising a positive electrode active material and a conductive agent.
9. The positive electrode material for lithium ion batteries according to claim 8,
the positive active material includes at least one of lithium nickelate, lithium manganate, lithium cobaltate, lithium manganese phosphate, lithium iron phosphate, lithium vanadium phosphate, lithium nickel cobalt aluminum oxide and lithium nickel cobalt manganese oxide.
10. The positive electrode material for lithium ion batteries according to claim 8,
the conductive agent includes at least one of acetylene black, carbon nanotubes, graphite, carbon black, graphene, and carbon fibers.
11. A positive electrode sheet for a lithium ion battery, characterized by the positive electrode material for a lithium ion battery according to any one of claims 1 to 10.
12. A lithium ion battery comprising the lithium ion battery positive electrode material according to any one of claims 1 to 10 or the lithium ion battery positive electrode sheet according to claim 11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010701142.6A CN111769287B (en) | 2020-07-20 | 2020-07-20 | Aqueous adhesive for battery, application of aqueous adhesive, lithium ion battery positive electrode material, lithium ion battery positive electrode sheet and lithium ion battery |
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|---|---|---|---|
| CN202010701142.6A CN111769287B (en) | 2020-07-20 | 2020-07-20 | Aqueous adhesive for battery, application of aqueous adhesive, lithium ion battery positive electrode material, lithium ion battery positive electrode sheet and lithium ion battery |
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| Publication Number | Publication Date |
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| CN111769287A CN111769287A (en) | 2020-10-13 |
| CN111769287B true CN111769287B (en) | 2021-11-05 |
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| CN102496714A (en) * | 2011-12-27 | 2012-06-13 | 天津力神电池股份有限公司 | Anode active substance, production method thereof, and lithium ion battery employing anode active substance |
| CN103370816A (en) * | 2011-02-14 | 2013-10-23 | 昭和电工株式会社 | Slurries obtained using binder for cell electrodes, electrodes obtained using slurries, and lithium-ion secondary cell obtained using electrodes |
| CN108155386A (en) * | 2018-01-24 | 2018-06-12 | 广州鹏辉能源科技股份有限公司 | Anode material for lithium-ion batteries, based lithium-ion battery positive plate and preparation method thereof and lithium ion battery |
| CN108461679A (en) * | 2018-02-28 | 2018-08-28 | 北京国能电池科技股份有限公司 | Lithium ion battery fixture, pressurization lithium ion battery and pressurization Li-ion batteries piles |
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| US5976731A (en) * | 1996-09-03 | 1999-11-02 | Fuji Photo Film Co., Ltd. | Non-aqueous lithium ion secondary battery |
| US20030062257A1 (en) * | 2001-10-03 | 2003-04-03 | Gozdz Antoni S. | Electrochemical cell comprising lamination of electrode and paper separator members |
| JP2010244936A (en) * | 2009-04-08 | 2010-10-28 | Sony Corp | Negative electrode, and nonaqueous electrolyte secondary battery |
| EP2738845A4 (en) * | 2011-07-29 | 2015-03-18 | Asahi Glass Co Ltd | Binder for electricity storage device |
| JP5713515B1 (en) * | 2013-08-06 | 2015-05-07 | 第一工業製薬株式会社 | Binder for electrode of lithium secondary battery, electrode manufactured using the binder, and lithium secondary battery using the electrode |
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| CN102496714A (en) * | 2011-12-27 | 2012-06-13 | 天津力神电池股份有限公司 | Anode active substance, production method thereof, and lithium ion battery employing anode active substance |
| CN108155386A (en) * | 2018-01-24 | 2018-06-12 | 广州鹏辉能源科技股份有限公司 | Anode material for lithium-ion batteries, based lithium-ion battery positive plate and preparation method thereof and lithium ion battery |
| CN108461679A (en) * | 2018-02-28 | 2018-08-28 | 北京国能电池科技股份有限公司 | Lithium ion battery fixture, pressurization lithium ion battery and pressurization Li-ion batteries piles |
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