CN111129457A - Aqueous ternary cathode slurry and preparation method thereof - Google Patents
Aqueous ternary cathode slurry and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a water-based ternary cathode slurry which comprises the following raw materials in parts by mass: 90-96 parts of ternary positive electrode active material, 2-5 parts of conductive agent, 2-5 parts of aqueous binder, 0.5-2 parts of thickening agent and 58-72 parts of deionized water; the aqueous binder is an acid-modified polyacrylamide binder. The aqueous ternary cathode slurry has the advantages that through the use of the acid-modified polyacrylamide binder, acid groups enable Li to be formed on the surface of the ternary cathode active material+Conducting electricityThe layer inhibits the reaction of the ternary positive active material and the electrolyte, reduces the pH value of the slurry, and can avoid the corrosion of alkaline substances in the electrolyte to a current collector of the positive pole piece after the positive pole piece is manufactured; the binder has stable electrochemical property, does not generate oxidation-reduction reaction in working voltage, is favorable for improving the cycle characteristic of the lithium ion battery, has good heat resistance, is not easy to decompose at high temperature, and can effectively improve the high-temperature storage performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to aqueous ternary cathode slurry and a preparation method thereof.
Background
Currently, lithium ion batteries mainly include lithium iron phosphate (LFP) batteries and ternary material batteries. The LFP battery system has good cycle performance and reliable safety performance, but has the problems of insufficient energy density and poor low-temperature performance, and particularly the problem of energy density becomes the main bottleneck of the development of the LFP battery system. The ternary material system comprises an NCM battery (nickel cobalt lithium manganate battery) or an NCA battery (nickel cobalt lithium aluminate battery) according to different element compositions. Ni and Mn with lower price are introduced into the NCM material, so that the use of Co is reduced, and the material cost is saved; on the other hand, the NCM can be in the voltage range of 4.35-4.6V, the structure of the NCM is kept stable, and reliable guarantee is provided for the NCM in a power battery system with high voltage and high energy density.
The prior art for producing the ternary lithium ion battery anode mainly adopts an oily system production process taking PVDF (polyvinylidene fluoride) and NMP (N-methyl pyrrolidone) as main materials, a great amount of NMP is used as a solvent in the production process of the ternary lithium ion battery anode, and NMP is used as a petrochemical industrial product, so that the ternary lithium ion battery anode has trace toxicity, and not only can cause environmental pollution due to discharge, but also can cause physiological (especially in the aspect of reproductive genetics) irreversible damage to production operation workers if reasonable protective measures are not taken. Meanwhile, the use of NMP directly influences the production process cost and the production safety of the lithium battery, and the production energy consumption and the cost investment are high.
At present, the production of lithium ion batteries is carried out by using an aqueous system, but because the specific surface area of ternary materials is large, the ternary materials in the system have large specific surface areaThe Ni element with stronger oxidizability can chemically react with the electrolyte, meanwhile, water in an aqueous system can damage the cathode material, particularly for a high-nickel cathode material, lithium ions of the Ni element are easy to dissolve out, the pH value of slurry is increased, the capacity of the slurry is reduced, a binder used in aqueous production is easy to decompose at high temperature, and the decomposition of the electrolyte is further caused, so that the performance of the battery, particularly the cycle performance and the high-temperature storage performance of the battery, is influenced. The water system production process of the ternary lithium ion positive electrode still has many defects, and the research and development in the field are less, and Chen is in' heated greener lithium-ion batteries0.4Co0.2Mn0.4O2CMC aqueous binder is adopted in the cathode material with super conductivity chemical performance', and the electric core produced by an aqueous system is found to have high rate characteristic and high cycle performance. Katsuya Kimura at "Improvement of the cyclic and heterocyclic effects of Li-Ion Batteries Using Li [ Ni ]0.8Co0.15Al0.05]O2CathodeContaining an Aqueous Binder with Pressurized CO2The Gas Treatment method adopts the step of introducing high-pressure CO into ternary anode slurry2Reaction with NCA surface base to form Li2CO3The aluminum foil can be inhibited from being corroded by alkali, and the cycle characteristic of the battery is improved; however, Li is formed2CO3It will still react with the electrolyte and affect the cycle characteristics of the battery. The novel water-based binder and the carbon-coated aluminum foil are adopted in the patent CN105762353A, so that the technical problem of the water-based high-nickel ternary positive electrode is solved, the charge and discharge performance of the battery is close to that of an oil-based technical positive electrode, alkaline substances in the positive electrode are effectively prevented from corroding the aluminum foil by using the carbon-coated aluminum foil, and the complexity of the manufacturing cost and the production process of the battery is increased. Patent 201710414118.2 discloses modifying a positive electrode material by adjusting the pH of slurry with an acidic aqueous solution, but the acidic aqueous solution is liable to destroy the structures of an aqueous binder and an aqueous thickener CMC, and the positive electrode material has a relatively high density, which is liable to cause sedimentation of the electrode slurry and is not favorable for the coating process. The crude chemical industries of Japan develop aqueous polyacrylamide PAM binders, and the pH of the binder solution is mainly neutralUsed on the separator and the negative electrode, and not used on the positive electrode.
Disclosure of Invention
Based on the above, the present invention provides an aqueous ternary positive electrode slurry, which is used to solve the technical problems of poor cycle characteristics, rate capability and high-temperature storage performance of ternary material batteries in the prior art.
The aqueous ternary cathode slurry comprises the following raw materials in parts by mass: the composite material comprises the following raw materials in parts by weight: 90-96 parts of ternary positive electrode active material, 2-5 parts of conductive agent, 2-5 parts of aqueous binder, 0.5-2 parts of thickening agent and 58-72 parts of deionized water; the aqueous binder is an acid-modified polyacrylamide binder.
According to the aqueous ternary cathode slurry, due to the use of the acid modified polyacrylamide binder, the acid groups are modified to form Li on the surface of the ternary cathode active material+The conducting layer inhibits the reaction of the ternary positive active material and the electrolyte, reduces the pH value of the slurry, and can avoid the corrosion of alkaline substances in the electrolyte to a current collector of the positive pole piece after the positive pole piece is manufactured; the binder has stable electrochemical property, does not generate oxidation-reduction reaction in working voltage, is favorable for improving the cycle characteristic of the lithium ion battery, has good heat resistance, is not easy to decompose at high temperature, and can effectively improve the high-temperature storage performance of the lithium ion battery.
Further, the structural formula of the modified polyacrylamide binder is as follows:
wherein, R1 is an unsaturated acid group selected from, but not limited to, one of an unsaturated carboxylic acid, an unsaturated sulfonic acid, or an unsaturated phosphoric acid.
Further, the unsaturated carboxylic acid is selected from but not limited to one of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
Further, the unsaturated sulfonic acid is selected from, but not limited to, one of (meth) acrylamide t-butyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, 2- (meth) acrylamide-2-hydroxypropane sulfonic acid, 3-sulfopropane (meth) acrylate, bis- (3-sulfopropyl) itaconate, and α -ethylenically unsaturated sulfonic acid such as vinyl sulfonic acid, styrene sulfonic acid, and (meth) propenyl sulfonic acid.
Further, the unsaturated phosphoric acid is selected from one of, but not limited to, vinyl phosphoric acid, vinyl phosphate, bis ((meth) acryloyloxyethyl) phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, dibutyl-2- (meth) acryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, monomethyl-2- (meth) acryloyloxyethyl phosphate, 3- (meth) acryloyloxy-2-hydroxypropane phosphoric acid.
Further, when in use, the aqueous binder is prepared into glue solution with solid content of 13.0-14.0%, and the pH value of the glue solution is 2.0-3.0.
Further, the ternary positive electrode active material is nickel cobalt lithium manganate or nickel cobalt lithium aluminate, and the mass ratio of nickel cobalt manganese or nickel cobalt aluminum is 3:3:3, 4:4:2, 5:3:2, 6:2:2 or 8:1: 1.
Further, the conductive agent is selected from one or more of conductive carbon black, carbon nano tube, carbon fiber, graphene and Ketjen black.
Further, the thickener is an aqueous thickener selected from, but not limited to, one or more combinations of sodium carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
In addition, the invention also provides a preparation method of the aqueous ternary cathode slurry, which comprises the following specific operation steps:
s1, adding a conductive agent and a ternary positive electrode active material into deionized water according to the formula proportion of any one of claims 1 to 9, and stirring the mixture uniformly to form slurry;
s2, adding the acid modified polyacrylamide binder with the formula amount into the slurry obtained in the step S1 for several times, and stirring the mixture evenly;
and S3, adding a thickening agent into the slurry obtained in the step S2, uniformly stirring, adding deionized water to adjust the viscosity of the slurry, vacuumizing to remove bubbles, and filtering to obtain the aqueous ternary cathode slurry.
Compared with the prior art, the aqueous ternary cathode slurry disclosed by the invention has the advantages that the unsaturated acid modified polyacrylamide binder is used, and the acid modification is adopted to form Li on the surface of the ternary cathode active material+The conducting layer reduces the pH value of the slurry, so that the ternary positive active material is better tightly attached to a pole piece current collector after the positive pole piece is manufactured, the reaction of the ternary positive active material and the electrolyte can be inhibited, and the corrosion of alkaline substances in the electrolyte to the pole piece current collector is effectively avoided; the modified group of the aqueous binder is further limited, the electrochemical performance of the aqueous binder is stable, the aqueous binder does not generate oxidation-reduction reaction in working voltage, and simultaneously contains imide group and hydroxyl group, so that the aqueous binder can generate thermal crosslinking reaction in the manufacturing process of the positive pole piece, the volume change of the positive pole material in the charging and discharging process is further inhibited, and the improvement of the cycle characteristic of the lithium ion battery is facilitated; the binder has good heat resistance, is not easy to decompose at high temperature, and can effectively improve the high-temperature storage performance of the lithium ion battery; in addition, the invention also limits the selection of other components, such as ternary cathode active materials, conductive agents and thickening agents, and optimizes the component proportion and the formula structure, so that the lithium ion battery prepared from the aqueous ternary cathode slurry has good high-temperature storage performance and high-temperature cycle performance. The preparation method has reasonable process arrangement, simple and convenient operation, high production efficiency and low cost.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic diagram illustrating a relationship between a capacity retention rate of a positive electrode sheet prepared from the aqueous ternary positive electrode slurry and a cycle number of a lithium ion battery.
Detailed Description
Example 1
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following componentsRaw materials in parts by weight: 9.0kg of ternary positive electrode active material, 0.2kg of conductive agent, 0.2kg of aqueous binder, 0.05kg of thickening agent and 5.8kg of deionized water; wherein the ternary positive electrode active material is LiNi0.8Co0.1Mn0.1O2The conductive agent is conductive carbon black, the thickening agent is hydroxyethyl cellulose, the aqueous binder is acrylamide-acrylic acid-allyl alcohol copolymer, and when the conductive carbon black is used, the conductive carbon black is prepared into glue solution with solid content of 13.0-14.0% in advance, and the pH value of the glue solution is 2.0-3.0.
Example 2
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following raw materials in parts by mass: 9.6kg of ternary positive electrode active material, 0.5kg of conductive agent, 0.5kg of aqueous binder, 0.1kg of thickening agent and 7.2kg of deionized water; wherein the ternary positive electrode active material is LiNi0.6Co0.2Mn0.2O2The conductive agent is carbon nano tube and carbon fiber, the thickening agent is sodium carboxymethylcellulose and hydroxypropyl cellulose, the aqueous binder is acrylamide-styrene sulfonic acid-allyl alcohol copolymer, and when the conductive agent is used, the conductive agent is prepared into glue solution with solid content of 13.0-14.0%, and the pH value of the glue solution is 2.0-3.0.
Example 3
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following raw materials in parts by mass: 9.3kg of ternary positive electrode active material, 0.45kg of conductive agent, 0.3kg of aqueous binder, 0.2kg of thickening agent and 6.0kg of deionized water; wherein the ternary positive electrode active material is LiNi0.8Co0.1Al0.1O2The conductive agent is carbon nano tube, graphene and Ketjen black, the thickening agent is hydroxyethyl cellulose, the aqueous binder is acrylamide-vinyl phosphoric acid-allyl alcohol, and the aqueous binder is prepared into a glue solution with the solid content of 13.0-14.0% in advance when in use, and the pH value of the glue solution is 2.0-3.0.
Example 4
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following raw materials in parts by mass: 3.5kg of ternary positive electrode active material, 0.131kg of conductive agent and water0.734kg of adhesive binder, 0.037kg of thickening agent and 2.1kg of deionized water; wherein the ternary positive electrode active material is LiNi0.8Co0.1Mn0.1O2The conductive agent is conductive carbon black, the thickening agent is sodium carboxymethylcellulose (CMC), the aqueous binder is acrylamide-acrylic acid-allyl alcohol copolymer, the aqueous binder is prepared into glue solution with solid content of 13.2% in advance when the adhesive is used, and the pH value of the glue solution is 2.0.
Example 5
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following raw materials in parts by mass: 3.5kg of ternary positive electrode active material, 0.131kg of conductive agent, 0.734kg of aqueous binder, 0.037kg of thickening agent and 2.1kg of deionized water; wherein the ternary positive electrode active material is LiNi0.8Co0.1Mn0.1O2The conductive agent is conductive carbon black, the thickening agent is sodium carboxymethylcellulose (CMC), the aqueous binder is acrylamide-styrene sulfonic acid-allyl alcohol copolymer, and the aqueous binder is prepared into glue solution with solid content of 13.2% in advance when in use, wherein the p H value of the glue solution is 2.0.
Example 6
The embodiment provides an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following raw materials in parts by mass: 3.5kg of ternary positive electrode active material, 0.131kg of conductive agent, 0.734kg of aqueous binder, 0.037kg of thickening agent and 2.1kg of deionized water; wherein the ternary positive electrode active material is LiNi0.8Co0.1Mn0.1O2The conductive agent is conductive carbon black, the thickening agent is sodium carboxymethylcellulose (CMC), the aqueous binder is acrylamide-vinyl phosphoric acid-allyl alcohol, and the aqueous binder is prepared into glue solution with the solid content of 13.2% in advance when the adhesive is used, and the pH value of the glue solution is 2.0.
Example 7
The embodiment provides a preparation method of an aqueous ternary cathode slurry for a lithium ion battery, which comprises the following specific operation steps:
s1, adding the conductive agent, the ternary positive electrode active material and the deionized water into a stirrer according to the formula proportion, and stirring for 0.5-2h to form slurry, wherein the revolution speed is 30rpm, and the rotation speed is 1500 rpm;
s2, adding the acid modified polyacrylamide binder with the formula amount into the slurry obtained in the step S1 for several times, and continuously stirring for 4-6h, wherein the revolution speed is 30rpm, and the rotation speed is 300 rpm;
and S3, adding the thickening agent into the slurry, stirring for 1-2h, wherein the revolution speed is 30rpm, the rotation speed is 1500rpm, then adding deionized water to adjust the viscosity of the slurry to 2000-5000 mPas, vacuumizing to remove bubbles, and filtering by a screen to obtain the aqueous anode slurry.
Example 8
The embodiment of the invention also provides a preparation method of the lithium ion battery, which comprises the following specific operation steps:
s1, preparing a positive pole piece: coating the prepared aqueous ternary positive electrode slurry on an aluminum foil of 10-25um by using a coating machine to prepare a positive electrode plate; the coating speed of the positive pole piece is 2-4 m/s; drying in 3 sections of drying ovens after coating, wherein the temperature of each section of drying oven is 60 ℃, 80 ℃ and 60 ℃ in sequence.
S2, sequentially drying, compacting, cutting and baking the prepared positive pole piece; wherein the compacting treatment is rolling with a roller press, and the compacting density is 3.4g/cm3(ii) a The drying treatment is vacuum drying at 85-95 deg.C for 12-24 hr.
S3, preparing the lithium ion battery: and preparing the lithium ion battery by using the prepared positive pole piece, the corresponding negative pole piece, the diaphragm and the electrolyte. The prepared lithium ion battery also comprises baking treatment before the electrolyte is injected.
Comparative example 1
Comparative example 1 was prepared, and comparative example 1 a positive electrode slurry was prepared using a conventional oily process: NMP was used as a solvent, PVDF was used as a binder, and other raw materials such as a ternary positive electrode active material, a conductive agent, and the like were the same as in examples 4 to 6. The prepared ternary cathode slurry was prepared according to the method described in example 8 to obtain a lithium ion battery.
According to the formula proportions of the examples 4 to 6, the corresponding lithium ion batteries are correspondingly prepared by the methods of the examples 7 and 8, the performance of the prepared lithium ion battery and the lithium ion battery prepared in the comparative example 1 are tested, and the test method and the results are as follows:
and (3) testing the peel strength of the positive electrode: the method for testing the peel strength of the positive pole piece adopted by the invention is a tensile tester method known by persons skilled in the art, and the test results are shown in table 1.
And (3) rate performance test: at normal temperature, the battery was fully charged at 1C (upper charge limit voltage 4.2V), and discharged at 1C, 2C, and 3C rates (lower discharge limit voltage 3.0V), and the test data are shown in table 1.
And (3) testing the cycle performance: the lithium ion battery obtained in example 4 was subjected to a cycle test at room temperature under a full charge at 1C (upper charge limit voltage 4.2V) and a discharge at 1C (lower discharge limit voltage 3.0V), and the test results are shown in fig. 1.
It is apparent from table 1 and fig. 1 that the peel strength of the positive electrode sheet prepared by using the aqueous binder (examples 4 to 6) provided by the present invention is significantly better than that of the positive electrode sheet of comparative example 1 using PVDF binder, and the gram capacity performance and rate capability of the battery cell positive electrode prepared by using the aqueous binder provided by the present invention are better than those of comparative example 1, mainly because the acidic binder and Li on the surface of the positive electrode material2CO3Reaction with LiOH to form Li+Conductive layer of Li+The aqueous binder used in the embodiment contains imide and hydroxyl, and in the process of manufacturing the positive electrode plate, the binder can generate a thermal crosslinking reaction and can inhibit the volume change of the high-nickel positive electrode material in the charging and discharging processes, so that the positive electrode material is prevented from cracking, and the cycle characteristic of the battery cell is improved.
Compared with the prior art, the aqueous ternary cathode slurry disclosed by the invention has the advantages that the unsaturated acid modified polyacrylamide binder is used, and the acid modification is adopted to form Li on the surface of the ternary cathode active material+Conductive layer, and reduces pH value of slurry, and the ternary positive active material is better after the positive pole piece is madeThe ground is tightly attached to the pole piece current collector, so that the reaction of the ternary positive active material and the electrolyte can be inhibited, and the corrosion of alkaline substances in the electrolyte to the pole piece current collector is effectively avoided; the modified group of the aqueous binder is further limited, the electrochemical performance of the aqueous binder is stable, the aqueous binder does not generate oxidation-reduction reaction in working voltage, and simultaneously contains imide group and hydroxyl group, so that the aqueous binder can generate thermal crosslinking reaction in the manufacturing process of the positive pole piece, the volume change of the positive pole material in the charging and discharging process is further inhibited, and the improvement of the cycle characteristic of the lithium ion battery is facilitated; the binder has good heat resistance, is not easy to decompose at high temperature, and can effectively improve the high-temperature storage performance of the lithium ion battery; in addition, the invention also limits the selection of other components, such as ternary cathode active materials, conductive agents and thickening agents, and optimizes the component proportion and the formula structure, so that the lithium ion battery prepared from the aqueous ternary cathode slurry has good high-temperature storage performance and high-temperature cycle performance. The preparation method has reasonable process arrangement, simple and convenient operation, high production efficiency and low cost.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The aqueous ternary cathode slurry is characterized by comprising the following raw materials in parts by mass: 90-96 parts of ternary positive electrode active material, 2-5 parts of conductive agent, 2-5 parts of aqueous binder, 0.5-2 parts of thickening agent and 58-72 parts of deionized water; the aqueous binder is an acid-modified polyacrylamide binder.
2. The high-nickel ternary positive electrode slurry according to claim 1, characterized in that: the structural formula of the acid modified polyacrylamide binder is as follows:
wherein, R1 is an unsaturated acid group selected from, but not limited to, one of an unsaturated carboxylic acid, an unsaturated sulfonic acid, or an unsaturated phosphoric acid.
3. The aqueous ternary positive electrode slurry according to claim 2, characterized in that: the unsaturated carboxylic acid is selected from but not limited to one of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
4. The aqueous ternary positive electrode slurry according to claim 2, wherein the unsaturated sulfonic acid is selected from the group consisting of (meth) acrylamide tert-butyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, 2- (meth) acrylamide-2-hydroxypropane sulfonic acid, 3-sulfopropane (meth) acrylate, bis- (3-sulfopropyl) itaconate, and α -ethylenically unsaturated sulfonic acid such as one of vinyl sulfonic acid, styrene sulfonic acid, and (meth) propenyl sulfonic acid.
5. The aqueous ternary positive electrode slurry according to claim 2, characterized in that: the unsaturated phosphoric acid is selected from one of but not limited to vinyl phosphoric acid, vinyl phosphate, bis ((meth) acryloyloxyethyl) phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, dibutyl-2- (meth) acryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, monomethyl-2- (meth) acryloyloxyethyl phosphate, 3- (meth) acryloyloxy-2-hydroxypropane phosphoric acid.
6. The aqueous ternary positive electrode slurry according to claim 2, characterized in that: when in use, the aqueous binder is prepared into glue solution with solid content of 13.0-14.0%, and the pH value of the glue solution is 2.0-3.0.
7. The aqueous ternary positive electrode slurry according to claim 1, characterized in that: the ternary positive electrode active material is nickel cobalt lithium manganate or nickel cobalt lithium aluminate, and the mass ratio of nickel cobalt manganese or nickel cobalt aluminum is 3:3:3, 4:4:2, 5:3:2, 6:2:2 or 8:1: 1.
8. The aqueous ternary positive electrode slurry according to claim 1, characterized in that: the conductive agent is selected from one or more of conductive carbon black, carbon nano tube, carbon fiber, graphene and Ketjen black.
9. The aqueous ternary positive electrode slurry according to claim 1, characterized in that: the thickener is an aqueous thickener selected from, but not limited to, one or more combinations of sodium hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
10. The preparation method of the aqueous ternary cathode slurry is characterized by comprising the following specific operation steps of:
s1, adding a conductive agent and a ternary positive electrode active material into deionized water according to the formula proportion of any one of claims 1 to 9, and stirring the mixture uniformly to form slurry;
s2, adding the acid modified polyacrylamide binder with the formula amount into the slurry obtained in the step S1 for several times, and stirring the mixture evenly;
and S3, adding a thickening agent into the slurry obtained in the step S2, uniformly stirring, adding deionized water to adjust the viscosity of the slurry, vacuumizing to remove bubbles, and filtering to obtain the aqueous ternary cathode slurry.
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