CN111063892A - Lithium ion battery cathode slurry and preparation method and application thereof - Google Patents
Lithium ion battery cathode slurry and preparation method and application thereof Download PDFInfo
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- 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
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- 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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- 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
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- 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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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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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- H—ELECTRICITY
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium ion battery cathode slurry and a preparation method and application thereof; the lithium ion battery cathode slurry adopts a specific raw material ratio, adopts any one or a combination of at least two of N-methyl pyrrolidone, N-dimethyl formamide or acetamide as a solvent, and adopts oxalic acid and/or citric acid as an additive; the negative pole piece prepared by the method has extremely low moisture content, and after the battery is assembled, the moisture content in the battery is reduced, so that the moisture content in the battery is reducedLiPF in electrolyte6The negative electrode slurry can improve the bonding strength between the negative electrode active material and the copper foil, and further improve the electrical property of the lithium ion battery after high-temperature storage; the preparation process of the lithium ion battery cathode slurry has a larger preparation process window, and hard carbon, graphite, lithium titanate or soft carbon can be used as a cathode active substance.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium ion battery cathode slurry, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high working voltage, wide working temperature range, environmental friendliness and the like, and is widely applied to the fields of 3C digital products, electric automobiles and the like. With the development of the technology, in order to meet certain special use environments, such as military industry or extreme high temperature environments, the battery is required to be capable of bearing a high temperature environment or circulation of 80-100 ℃, and the battery is required to have higher high temperature storage capacity and high temperature cycle resistance.
When the lithium ion battery is stored at high temperature, the LiPF can be accelerated due to the existence of moisture6So that the high-temperature performance of the lithium ion battery is reduced; in addition, the adhesion of the negative active material to the copper foil gradually decreases during high-temperature storage, reducing the electrical performance of the lithium ion battery. The high-quality cathode slurry is a necessary condition for obtaining the lithium ion battery with excellent performance; therefore, it is very important to obtain a cathode slurry with uniformly dispersed components and good stability.
CN107834023A discloses an aqueous negative electrode slurry, which is prepared by adding low-polarity ethylene carbonate to effectively adjust the dispersibility of negative active materials and conductive agents in deionized water, so that the components of the slurry are uniformly dispersed, and particle agglomeration is reduced or even avoided.
CN106169559A discloses a preparation method of low-temperature and high-rate negative electrode slurry, which adopts hard carbon and artificial graphite as main materials, firstly prepares N-methyl pyrrolidone solution of polyvinylidene fluoride, and then sequentially adds a conductive agent, the hard carbon, the graphite and oxalic acid.
Therefore, the development of the negative electrode slurry which can obviously reduce the moisture content in the negative electrode plate and the obtained lithium ion battery has high-temperature resistance and the preparation method thereof still have important significance.
Disclosure of Invention
The invention aims to provide a lithium ion battery cathode slurry and a preparation method and application thereof; the lithium ion battery cathode slurry adopts a specific raw material ratio, adopts any one or a combination of at least two of N-methyl pyrrolidone, N-dimethyl formamide or acetamide as a solvent, and adopts oxalic acid and/or citric acid as an additive; the negative pole piece prepared from the lithium ion battery anode material has extremely low moisture content, and after the battery is assembled, the moisture content in the battery is reduced, so that LiPF in electrolyte is reduced6The negative electrode slurry can improve the bonding strength between the negative electrode active material and the copper foil, and further improve the electrical property of the lithium ion battery after high-temperature storage; the preparation method of the lithium ion battery cathode slurry has a large preparation process window, and hard carbon, graphite, lithium titanate or soft carbon can be used as a cathode active substance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium ion battery negative electrode slurry, which comprises the following components in parts by weight:
the additive comprises oxalic acid and/or citric acid; the solvent includes any one of N-methylpyrrolidone, N-dimethylformamide or acetamide, or a combination of at least two thereof, which illustratively includes a combination of N-methylpyrrolidone and N, N-dimethylformamide, a combination of acetamide and N-methylpyrrolidone, or a combination of N, N-dimethylformamide and acetamide, and the like.
The lithium ion battery negative electrode slurry comprises, by weight, 87-92.5 parts, such as 88 parts, 89 parts, 90 parts, 91 parts, 92 parts and the like of a negative electrode active material, 0.1-5 parts, such as 0.5 part, 1 part, 2 parts, 3 parts, 4 parts and the like of a conductive agent, 2-5 parts, such as 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts and the like of a binder, 0.1-2 parts, such as 0.5 part, 1 part, 1.5 parts and the like of a surfactant, 0.1-1 part, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part and the like of an additive, 87-100 parts, such as 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts and the like of a solvent.
The lithium ion battery negative electrode slurry provided by the invention adopts any one or a combination of at least two of N-methyl pyrrolidone, N-dimethyl formamide or acetamide as a solvent, adopts oxalic acid and/or citric acid as an additive, and is matched with a specific raw material proportion, so that the water content of a negative electrode piece prepared from the negative electrode slurry is extremely low and can reach below 40ppm, and the surface active agent is added into the negative electrode slurry, so that the surface tension of the solvent can be reduced, the sufficient wetting of a negative electrode active substance is facilitated, the agglomeration of the negative electrode active substance in the negative electrode slurry is reduced, and the dispersion of each component in the negative electrode slurry is facilitated.
The additive is added into the negative electrode slurry, so that the adhesion force of the negative electrode active material and the copper foil can be increased, and the electrical property of the lithium ion battery after high-temperature storage can be improved.
The lithium ion battery cathode slurry is used for a high-temperature-resistant lithium ion battery.
Preferably, the negative active material includes any one of or a combination of at least two of hard carbon, graphite, lithium titanate, or soft carbon, and the combination exemplarily includes a combination of hard carbon and graphite, a combination of soft carbon and hard carbon, or a combination of graphite and soft carbon, and the like.
Preferably, the conductive agent includes any one of conductive carbon black, conductive graphite or graphene, or a combination of at least two of them, and the combination exemplarily includes a combination of conductive carbon black and conductive graphite, a combination of graphene and conductive carbon black, or a combination of conductive graphite and graphene, and the like.
As the conductive carbon black, conductive carbon black SP can be used, and as the conductive graphite, conductive graphite KS-6 can be used.
Preferably, the binder comprises polyvinylidene fluoride.
Preferably, the surfactant comprises Ethylene Carbonate (EC) and/or diethyl carbonate (DEC).
Preferably, the additive is oxalic acid.
According to the additive, oxalic acid is adopted, under the action of the oxalic acid, carboxyl functional groups on the surface of the negative active material are increased and can react with hydroxyl in the binder, so that the adhesion between the negative active material and the copper foil is increased, after high-temperature storage, the adhesion is increased, and the electrical property of the lithium ion battery is improved.
Preferably, the solvent is N-methylpyrrolidone.
In a second aspect, the present invention provides a method for preparing a lithium ion battery negative electrode slurry according to the first aspect, the method comprising the steps of:
(1) preparing glue: mixing the binder and part of the solvent according to the weight ratio to obtain a glue solution;
(2) mixing materials: mixing the negative active material, the conductive agent and the surfactant according to the weight ratio to obtain a mixture;
(3) kneading: adding 50-70 wt%, such as 53 wt%, 55 wt%, 58 wt%, 60 wt%, 63 wt%, 65 wt% or 68 wt% of the glue solution in the step (1) into the mixture in the step (2), and mixing;
(4) pulping: adding 15-25 wt%, such as 16 wt%, 18 wt%, 20 wt%, 22 wt% or 24 wt% of the glue solution in step (1) to the product in step (3), adding the rest solvent and additives, and mixing;
(5) homogenizing: adding 15-25 wt%, such as 16 wt%, 18 wt%, 20 wt%, 22 wt% or 24 wt% of the glue solution in the step (1) into the product in the step (4), mixing, and sieving to obtain the slurry;
the weight ratio of the binder to the partial solvent in step (1) is 1: 10-12, such as 1:10, 1:10.5, 1:11, 1:11.5, or 1:12, etc., the additive includes oxalic acid and/or citric acid, the solvent includes any one of N-methylpyrrolidone, N-dimethylformamide, or acetamide, or a combination of at least two thereof, which illustratively includes a combination of N-methylpyrrolidone and N, N-dimethylformamide, a combination of acetamide and N-methylpyrrolidone, or a combination of N, N-dimethylformamide and acetamide, etc.
In the preparation process of the lithium ion battery cathode slurry, the glue solution is added in the step (3), and the surface tension of the solvent is reduced under the action of the surfactant, so that the surface of the cathode active material is soaked with the solvent.
Preferably, the mixing in step (1) is carried out by stirring at a linear speed of 6 to 10m/s, such as 7m/s, 8m/s or 9 m/s.
Preferably, the mixing time in step (1) is 2.5-3.5h, such as 2.6h, 2.8h, 3h, 3.2h or 3.4h, etc.
Preferably, the mixing in step (2) is carried out by stirring at a linear velocity of 0.5 to 1m/s, such as 0.6m/s, 0.7m/s, 0.8m/s or 0.9m/s, etc.
Preferably, the mixing in step (2) is for a time of 1.5-2.5h, such as 1.6h, 1.8h, 2h, 2.2h, 2.4h, etc.
Preferably, the gum solution in step (3) is added in n portions, where n is 2 or more, such as 2, 3, 4, 5 or 6, etc., preferably 2 to 3.
Preferably, n is 2, in the step (3), 25-35 wt% of glue solution of the glue solution in the step (1) is added into the mixed material in the step (2) and mixed, and then, 25-35 wt% of glue solution of the glue solution in the step (1) is added again and mixed.
The adding process of the glue solution adopts the steps, wherein after the glue solution is added for the first time, the surface tension of the solvent is reduced under the action of the surfactant, so that the surface of the negative active material is soaked with the solvent; and adding the glue solution for the second time, and fully soaking the negative active material by using the solvent in the glue solution to further improve the mixing uniformity of all components in the negative slurry.
Preferably, the mixing in step (3) is carried out by stirring at a linear speed of 1 to 2m/s, such as 1.2m/s, 1.5m/s or 1.8m/s, etc.
Preferably, the mixing in step (3) is for a time of 0.5-2h, such as 0.8h, 1h, 1.2h, 1.5h, 1.8h, etc.
Preferably, the mixing method in step (4) is stirring, and the mixing process is performed under vacuum.
Preferably, the mixing time in step (4) is 2-4h, such as 2.2h, 2.5h, 2.8h, 3h, 3.5h or 3.8h, etc.
Preferably, the mixing method in step (5) is stirring, and the mixing process is performed under vacuum.
Preferably, the vacuum conditions have a vacuum of ≦ -0.08MPa, such as-0.085 MPa, -0.09MPa, or-0.095 MPa, and the like.
Preferably, the mesh number of the sieve of step (5) is 120-150 mesh, such as 125 mesh, 130 mesh, 135 mesh, 140 mesh or 145 mesh.
As a preferred technical scheme of the present invention, the preparation method of the lithium ion battery negative electrode slurry comprises the following steps:
(1) preparing glue: mixing the binder and part of the solvent according to the weight ratio, stirring for 2.5-3.5h under the condition that the linear speed is 6-10m/s to obtain a glue solution, and standing;
(2) mixing materials: mixing the negative active material, the conductive agent and the surfactant according to the weight ratio, and mixing for 1.5-2.5 hours under the condition that the linear speed is 0.5-1m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 25-35 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.25-0.75h under the condition of the linear speed of 1-2m/s, then adding the glue solution accounting for 25-35 wt% of the glue solution in the step (1) again, and stirring for 0.25-0.75h under the condition of the linear speed of 1-2 m/s;
(4) pulping: adding 15-25 wt% of glue solution of the glue solution in the step (1) into the product of the step (3), then adding the residual solvent and the additive, stirring for 2-4h under the condition that the linear speed is 2-3m/s, wherein the vacuum degree in the stirring process is less than or equal to-0.08 MPa;
(5) homogenizing: adding 15-25 wt% of glue solution in the step (1) into the product in the step (4), stirring for 2-3h under the condition that the linear speed is 2-3m/s, wherein the vacuum degree in the stirring process is less than or equal to-0.08 MPa, and then sieving to obtain the slurry;
the weight ratio of the binder to part of the solvent in the step (1) is 1 (10-12), the additive comprises oxalic acid and/or citric acid, and the solvent comprises any one or the combination of at least two of N-methylpyrrolidone, N-dimethylformamide or acetamide.
In a third aspect, the invention provides a negative electrode plate of a lithium ion battery, wherein the negative electrode plate adopts the negative electrode slurry in the first aspect.
In a fourth aspect, the invention provides a method for preparing a negative electrode plate of a lithium ion battery according to the third aspect, the method comprises coating the two sides of a negative electrode slurry on a current collector, and then drying to obtain the negative electrode plate of the lithium ion battery; the negative electrode slurry is the lithium ion battery negative electrode slurry in the first aspect.
Preferably, the drying is step drying.
Preferably, the temperature of the step drying is 80-90 ℃, 95-120 ℃ and 80-90 ℃ in sequence.
The drying process of the invention is carried out in three stages, wherein the drying temperature of the first stage is 80-90 ℃, such as 82 ℃, 84 ℃, 86 ℃ or 88 ℃ and the like; the second stage drying temperature is 95-120 deg.C, such as 96 deg.C, 98 deg.C, 100 deg.C, 105 deg.C, 110 deg.C or 115 deg.C, etc., and the third stage drying temperature is 80-90 deg.C, such as 82 deg.C, 84 deg.C, 86 deg.C or 88 deg.C, etc.
Preferably, the belt speed of the step drying is 10-20m/s, such as 11m/s, 13m/s, 15m/s, 17m/s or 19 m/s.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lithium ion battery cathode slurry provided by the invention adopts any one or the combination of at least two of N-methyl pyrrolidone, N-dimethylformamide or acetamide as a solvent, so that the residual moisture of a cathode pole piece is reduced, and a foundation is laid for the subsequent low moisture content; the lithium ion battery cathode slurry is used for preparing a cathode pole piece, the moisture content in the obtained cathode pole piece can reach below 40ppm, and the moisture content is reduced after the battery is assembledInternal moisture content of battery, reduced LiPF6The decomposition of the lithium ion battery improves the stability of the lithium ion battery stored at high temperature (for example, 80 ℃);
(2) the surface active agent is added into the lithium ion battery cathode slurry, and under the action of the surface active agent, the surface tension of the solvent is reduced, so that the surface of the cathode active material is fully soaked by the solvent, the agglomeration of the cathode active material in the cathode slurry is reduced, and the dispersion of each component in the cathode slurry is facilitated;
(3) according to the lithium ion battery negative electrode slurry, the oxalic acid and/or the citric acid is added to serve as the additive, the number of carboxyl functional groups on the surface of the negative electrode active material can be increased, the carboxyl functional groups react with hydroxyl in the binder, the adhesion force between the negative electrode active material and the copper foil is increased, after the lithium ion battery negative electrode slurry is stored at a high temperature, the adhesion force is increased, and the electrical property is improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The negative electrode slurry comprises the following components in parts by weight:
wherein the negative active material consists of hard carbon and graphite in a mass ratio of 1: 1;
the conductive agent is SP; the surfactant is EC, the additive is oxalic acid, the binder is polyvinylidene fluoride, and the solvent is N-methyl pyrrolidone;
the preparation method of the anode slurry comprises the following steps:
(1) preparing glue: mixing 5 parts of binder and 57.5 parts of solvent, stirring for 3 hours under the condition that the linear speed is 8m/s to obtain glue solution, and standing for later use;
(2) mixing materials: mixing 87 parts of negative electrode active material, 5 parts of conductive agent and 2 parts of surfactant for 2 hours under the condition that the linear speed is 1m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 30 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.5h under the condition that the linear speed is 1m/s, then adding the glue solution accounting for 30 wt% of the glue solution in the step (1) again, and stirring for 0.5h under the condition that the linear speed is 1 m/s;
(4) pulping: adding 20 wt% of glue solution in the step (1) into the product in the step (3), then adding 30.5 parts of solvent and 1 part of additive, stirring for 3 hours under the condition that the linear speed is 2m/s, and keeping the vacuum degree at-0.08 MPa in the stirring process;
(5) homogenizing: and (3) adding the glue solution which accounts for 20 wt% of the glue solution in the step (1) into the product in the step (4), stirring for 2.5h under the condition that the linear speed is 2m/s, keeping the vacuum degree at-0.08 MPa in the stirring process, then sieving by using a 120-mesh sieve to obtain the negative electrode slurry, and recording the state of the negative electrode slurry.
The negative electrode slurry obtained in the example was used for preparing a negative electrode plate, and the method was as follows:
(a) adding the negative electrode slurry prepared in the embodiment into a sample pool which is continuously stirred, adjusting the coating thickness, and performing double-sided coating by adopting an extrusion type coating machine;
(b) drying the pole piece obtained in the step (a), wherein the drying process is divided into three stages, and the temperature of the three drying stages is 85 ℃, 115 ℃ and 85 ℃ in sequence; the tape-moving speed is 12 m/s;
and then rolling, slitting and drying to obtain the negative pole piece of the embodiment.
Example 2
The negative electrode slurry comprises the following components in parts by weight:
wherein the negative active material consists of hard carbon, graphite and soft carbon in a mass ratio of 2:1: 1; the conductive agent is graphene; the surface active agent is DEC, the additive is citric acid, the binder is polyvinylidene fluoride, and the solvent is N-methyl pyrrolidone;
the preparation method of the anode slurry comprises the following steps:
(1) preparing glue: mixing 4.4 parts of binder and 50.6 parts of solvent, stirring for 3 hours under the condition that the linear speed is 10m/s to obtain glue solution, and standing for later use;
(2) mixing materials: mixing 92.5 parts of negative active material, 0.1 part of conductive agent and 2 parts of surfactant for 2 hours under the condition that the linear speed is 1m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 30 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.5h under the condition that the linear speed is 2m/s, then adding the glue solution accounting for 30 wt% of the glue solution in the step (1) again, and stirring for 0.5h under the condition that the linear speed is 1 m/s;
(4) pulping: adding 20 wt% of glue solution in the step (1) into the product in the step (3), then adding 49.4 parts of solvent and 1 part of additive, stirring for 3 hours under the condition that the linear speed is 3m/s, and keeping the vacuum degree at-0.08 MPa in the stirring process;
(5) homogenizing: and (3) adding the glue solution which accounts for 20 wt% of the glue solution in the step (1) into the product in the step (4), stirring for 2.5h under the condition that the linear speed is 2.5m/s, keeping the vacuum degree at-0.08 MPa in the stirring process, then sieving by using a 120-mesh sieve to obtain the negative electrode slurry, and recording the state of the negative electrode slurry.
The negative electrode slurry obtained in the example was used for preparing a negative electrode plate, and the method was as follows:
(a) adding the negative electrode slurry prepared in the embodiment into a sample pool which is continuously stirred, adjusting the coating thickness, and performing double-sided coating by adopting an extrusion type coating machine;
(b) drying the pole piece obtained in the step (a), wherein the drying process is divided into three stages, and the temperature of the three drying stages is 90 ℃, 120 ℃ and 90 ℃ in sequence; the tape-moving speed is 10 m/s;
and then rolling, slitting and drying to obtain the negative pole piece of the embodiment.
Example 3
The negative electrode slurry comprises the following components in parts by weight:
wherein the negative active material is composed of graphite; the conductive agent is formed by mixing graphene and KS-6 in a mass ratio of 1: 1; the surfactant is prepared from the following components in a mass ratio of 1:1 EC and DEC, wherein the additive is prepared by mixing the following components in a ratio of 1:1, mixing oxalic acid and citric acid, wherein the binder is polyvinylidene fluoride, and the solvent is N-methyl pyrrolidone;
the preparation method of the anode slurry comprises the following steps:
(1) preparing glue: mixing 3 parts of binder and 34.5 parts of solvent, stirring for 3 hours under the condition that the linear speed is 8m/s to obtain glue solution, and standing for later use;
(2) mixing materials: mixing 90 parts of negative electrode active material, 5 parts of conductive agent and 1 part of surfactant, and mixing for 2 hours under the condition that the linear speed is 0.5m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 30 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.5h under the condition that the linear speed is 1.5m/s, then adding the glue solution accounting for 30 wt% of the glue solution in the step (1) again, and stirring for 0.5h under the condition that the linear speed is 1.5 m/s;
(4) pulping: adding 20 wt% of glue solution in the step (1) into the product in the step (3), then adding 55.5 parts of solvent and 1 part of additive, stirring for 3 hours under the condition that the linear speed is 2.5m/s, and keeping the vacuum degree at-0.08 MPa in the stirring process;
(5) homogenizing: and (3) adding the glue solution which accounts for 20 wt% of the glue solution in the step (1) into the product in the step (4), stirring for 2.5h under the condition that the linear speed is 2m/s, keeping the vacuum degree at-0.08 MPa in the stirring process, then sieving by using a 120-mesh sieve to obtain the negative electrode slurry, and recording the state of the negative electrode slurry.
The negative electrode slurry obtained in the example was used for preparing a negative electrode plate, and the method was as follows:
(a) adding the negative electrode slurry prepared in the embodiment into a sample pool which is continuously stirred, adjusting the coating thickness, and performing double-sided coating by adopting an extrusion type coating machine;
(b) drying the pole piece obtained in the step (a), wherein the drying process is divided into three stages, and the temperature of the three drying stages is 85 ℃, 115 ℃ and 85 ℃ in sequence; the tape-moving speed is 15 m/s;
and then rolling, slitting and drying to obtain the negative pole piece of the embodiment.
Example 4
The negative electrode slurry comprises the following components in parts by weight:
wherein the negative electrode active material is composed of soft carbon; the conductive agent is formed by mixing graphene and SP in a mass ratio of 1: 1; the surfactant is EC, the additive is oxalic acid, the binder is polyvinylidene fluoride, and the solvent is N-methyl pyrrolidone;
the preparation method of the anode slurry comprises the following steps:
(1) preparing glue: mixing 2.6 parts of binder and 29.9 parts of solvent, stirring for 3 hours under the condition that the linear speed is 9m/s to obtain glue solution, and standing for later use;
(2) mixing materials: mixing 91 parts of negative active material, 3.8 parts of conductive agent and 1.8 parts of surfactant, and mixing for 2 hours under the condition that the linear speed is 0.8m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 30 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.5h under the condition that the linear speed is 1.5m/s, then adding the glue solution accounting for 30 wt% of the glue solution in the step (1) again, and stirring for 0.5h under the condition that the linear speed is 1.5 m/s;
(4) pulping: adding 20 wt% of glue solution in the step (1) into the product in the step (3), then adding 60.1 parts of solvent and 0.8 part of additive, stirring for 3 hours under the condition that the linear speed is 2.2m/s, and keeping the vacuum degree at-0.08 MPa in the stirring process;
(5) homogenizing: and (3) adding the glue solution which accounts for 20 wt% of the glue solution in the step (1) into the product in the step (4), stirring for 3 hours under the condition that the linear speed is 2.3m/s, keeping the vacuum degree at-0.08 MPa in the stirring process, then sieving by using a 120-mesh sieve to obtain the negative electrode slurry, and recording the state of the negative electrode slurry.
The negative electrode slurry obtained in the example was used for preparing a negative electrode plate, and the method was as follows:
(a) adding the negative electrode slurry prepared in the embodiment into a sample pool which is continuously stirred, adjusting the coating thickness, and performing double-sided coating by adopting an extrusion type coating machine;
(b) drying the pole piece obtained in the step (a), wherein the drying process is divided into three stages, and the temperature of the three drying stages is 90 ℃, 105 ℃ and 90 ℃ in sequence; the tape-moving speed is 10 m/s;
and then rolling, slitting and drying to obtain the negative pole piece of the embodiment.
Example 5
The negative electrode slurry comprises the following components in parts by weight:
wherein the negative active material consists of hard carbon, graphite and soft carbon in a mass ratio of 1:1: 1; the conductive agent is SP; the surfactant is EC, the additive is citric acid, the binder is polyvinylidene fluoride, and the solvent is N-methylpyrrolidone;
the preparation method of the anode slurry comprises the following steps:
(1) preparing glue: mixing 3.3 parts of binder and 38 parts of solvent, stirring for 3 hours under the condition that the linear speed is 7m/s to obtain glue solution, and standing for later use;
(2) mixing materials: mixing 91 parts of negative active material, 3.5 parts of conductive agent and 1.9 parts of surfactant, and mixing for 2 hours at the linear speed of 0.75m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 30 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.5h under the condition that the linear speed is 1.3m/s, then adding the glue solution accounting for 30 wt% of the glue solution in the step (1) again, and stirring for 0.5h under the condition that the linear speed is 1.2 m/s;
(4) pulping: adding 20 wt% of glue solution in the step (1) into the product in the step (3), then adding 57 parts of solvent and 0.3 part of additive, stirring for 3 hours under the condition that the linear speed is 2.3m/s, and keeping the vacuum degree at-0.08 MPa in the stirring process;
(5) homogenizing: and (3) adding the glue solution which accounts for 20 wt% of the glue solution in the step (1) into the product in the step (4), stirring for 3 hours under the condition that the linear speed is 2.3m/s, keeping the vacuum degree at-0.08 MPa in the stirring process, then sieving by using a 120-mesh sieve to obtain the negative electrode slurry, and recording the state of the negative electrode slurry.
The negative electrode slurry obtained in the example was used for preparing a negative electrode plate, and the method was as follows:
(a) adding the negative electrode slurry prepared in the embodiment into a sample pool which is continuously stirred, adjusting the coating thickness, and performing double-sided coating by adopting an extrusion type coating machine;
(b) drying the pole piece obtained in the step (a), wherein the drying process is divided into three stages, and the temperatures of the three drying stages are 80 ℃, 120 ℃ and 90 ℃ in sequence; the tape-moving speed is 15 m/s;
and then rolling, slitting and drying to obtain the negative pole piece of the embodiment.
Comparative example 1
The present example is different from example 1 in that the mass of the binder and the like was replaced with an aqueous binder SBR, and a negative electrode slurry was prepared by an aqueous process, and the other conditions were completely the same as those of example 1.
Comparative example 2
The difference between this example and example 1 is that the operations in step (3) and step (4) are not performed, and the glue solution, solvent and additives are added to the mixture in step (2) in step (5), and the other conditions are exactly the same as those in example 1.
Comparative example 3
This example differs from example 1 in that no surfactant was added during the preparation and the other conditions were exactly the same as in example 1.
Comparative example 4
This example differs from example 1 in that no additives were added during the preparation and the other conditions were exactly the same as in example 1.
And (3) performance testing:
testing the water content of the negative pole pieces prepared by the methods of examples 1-5 and comparative examples 1-4, assembling the negative pole pieces and corresponding positive pole pieces into a full cell, performing a storage test at 80 ℃ after formation, and testing the capacity recovery rate of the full cell; the test results are shown in table 1;
in a high-temperature storage test at 80 ℃, the storage time when the storage voltage of the lithium ion battery is more than 3V is recorded as effective storage time, and the recorded storage time is shown in the following table 1;
TABLE 1
As can be seen from the table above, the cathode slurry is not easy to agglomerate, and the moisture content in the cathode pole piece prepared from the cathode slurry is extremely low and can be controlled below 40 ppm; and the high-temperature storage performance of the battery is obviously improved, and when the lithium ion battery is stored for more than 1300 hours at the temperature of 80 ℃, the capacity recovery rate is more than 96 percent.
Comparing example 1 with comparative example 1, it can be seen that, by using the water-based binder SBR instead of the binder and using the water-based process, the moisture content in the obtained negative electrode plate is greater than 100ppm, which may adversely affect the high-temperature storage performance of the battery.
Comparing example 1 and comparative example 2, it can be seen that the kneading and pulping steps described in the present application are not adopted in the preparation process of the negative electrode slurry, and agglomeration is easily generated in the prepared product, thereby affecting the electrical properties of the lithium ion battery.
Comparing example 1 with comparative examples 3 to 4, it can be seen that the addition of the surfactant and the additive in the conductive paste according to the present invention plays an important role in improving the high temperature storage performance of the lithium ion battery.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The lithium ion battery negative electrode slurry is characterized by comprising the following components in parts by weight:
the additive comprises oxalic acid and/or citric acid; the solvent comprises any one or the combination of at least two of N-methyl pyrrolidone, N-dimethyl formamide or acetamide.
2. The lithium ion battery negative electrode slurry of claim 1, wherein the negative electrode active material comprises any one of or a combination of at least two of hard carbon, graphite, lithium titanate, or soft carbon;
preferably, the conductive agent comprises any one of or a combination of at least two of conductive carbon black, conductive graphite or graphene;
preferably, the binder comprises polyvinylidene fluoride;
preferably, the surfactant comprises ethylene carbonate and/or diethyl carbonate;
preferably, the additive is oxalic acid;
preferably, the solvent is N-methylpyrrolidone.
3. The method for preparing the lithium ion battery negative electrode slurry according to claim 1 or 2, wherein the method comprises the steps of:
(1) preparing glue: mixing the binder and part of the solvent according to the weight ratio to obtain a glue solution;
(2) mixing materials: mixing the negative active material, the conductive agent and the surfactant according to the weight ratio to obtain a mixture;
(3) kneading: adding 50-70 wt% of the glue solution in the step (1) into the mixture in the step (2), and mixing;
(4) pulping: adding 15-25 wt% of glue solution of the glue solution in the step (1) into the product in the step (3), then adding the rest solvent and the additive, and mixing;
(5) homogenizing: adding 15-25 wt% of glue solution of the glue solution in the step (1) into the product in the step (4), mixing and sieving to obtain the slurry;
the weight ratio of the binder to part of the solvent in the step (1) is 1 (10-12), the additive comprises oxalic acid and/or citric acid, and the solvent comprises any one or the combination of at least two of N-methylpyrrolidone, N-dimethylformamide or acetamide.
4. The method according to claim 1, wherein the mixing in step (1) is performed by stirring at a linear velocity of 6 to 10 m/s;
preferably, the mixing time of step (1) is 2.5-3.5 h.
5. The method according to claim 3 or 4, wherein the mixing in step (2) is performed by stirring at a linear velocity of 0.5 to 1 m/s;
preferably, the mixing time in step (2) is 1.5-2.5 h.
6. The method according to any one of claims 3 to 5, wherein the glue solution in step (3) is added in n portions, wherein n is greater than or equal to 2, preferably 2 to 3;
preferably, n is 2, adding glue solution accounting for 25-35 wt% of the glue solution in the step (1) into the mixture in the step (2) in the step (3), mixing, adding glue solution accounting for 25-35 wt% of the glue solution in the step (1) again, and mixing;
preferably, the mixing method in the step (3) is stirring, and the linear speed of the stirring is 1-2 m/s;
preferably, the mixing time in step (3) is 0.5-2 h;
preferably, the mixing method in the step (4) is stirring, and the mixing process is carried out under vacuum conditions;
preferably, the mixing time in the step (4) is 2-4 h;
preferably, the mixing method in step (5) is stirring, and the mixing process is carried out under vacuum conditions;
preferably, the vacuum degree of the vacuum condition is less than or equal to-0.08 MPa;
preferably, the mesh number of the sieved screen in the step (5) is 120-150 meshes.
7. A method according to any of claims 3-6, characterized in that the method comprises the steps of:
(1) preparing glue: mixing the binder and part of the solvent according to the weight ratio, stirring for 2.5-3.5h under the condition that the linear speed is 6-10m/s to obtain a glue solution, and standing;
(2) mixing materials: mixing the negative active material, the conductive agent and the surfactant according to the weight ratio, and mixing for 1.5-2.5 hours under the condition that the linear speed is 0.5-1m/s to obtain a mixture;
(3) kneading: adding the glue solution accounting for 25-35 wt% of the glue solution in the step (1) into the mixture in the step (2), stirring for 0.25-0.75h under the condition of the linear speed of 1-2m/s, then adding the glue solution accounting for 25-35 wt% of the glue solution in the step (1) again, and stirring for 0.25-0.75h under the condition of the linear speed of 1-2 m/s;
(4) pulping: adding 15-25 wt% of glue solution of the glue solution in the step (1) into the product of the step (3), then adding the residual solvent and the additive, stirring for 2-4h under the condition that the linear speed is 2-3m/s, wherein the vacuum degree in the stirring process is less than or equal to-0.08 MPa;
(5) homogenizing: adding 15-25 wt% of glue solution in the step (1) into the product in the step (4), stirring for 2-3h under the condition that the linear speed is 2-3m/s, wherein the vacuum degree in the stirring process is less than or equal to-0.08 MPa, and then sieving to obtain the slurry;
the weight ratio of the binder to part of the solvent in the step (1) is 1 (10-12), the additive comprises oxalic acid and/or citric acid, and the solvent comprises any one or the combination of at least two of N-methylpyrrolidone, N-dimethylformamide or acetamide.
8. A lithium ion battery negative pole piece is characterized in that the negative pole slurry as claimed in claim 1 or 2 is adopted in the negative pole piece.
9. The preparation method of the lithium ion battery negative electrode piece according to claim 8, wherein the method comprises coating the negative electrode slurry on a current collector on both sides, and then drying to obtain the lithium ion battery negative electrode piece; the negative electrode slurry adopts the negative electrode slurry of the lithium ion battery as claimed in claim 1 or 2.
10. The method of claim 9, wherein said drying is step drying;
preferably, the temperature of the step-by-step drying is 80-90 ℃, 95-120 ℃ and 80-90 ℃ in sequence;
preferably, the tape speed of the step drying process is 10-20 m/s.
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