CN117613201A - Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery - Google Patents

Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery Download PDF

Info

Publication number
CN117613201A
CN117613201A CN202311631560.2A CN202311631560A CN117613201A CN 117613201 A CN117613201 A CN 117613201A CN 202311631560 A CN202311631560 A CN 202311631560A CN 117613201 A CN117613201 A CN 117613201A
Authority
CN
China
Prior art keywords
lithium ion
ion battery
cmc
graphite
slurry
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311631560.2A
Other languages
Chinese (zh)
Inventor
陆俊
刘静杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN202311631560.2A priority Critical patent/CN117613201A/en
Publication of CN117613201A publication Critical patent/CN117613201A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lithium ion battery technology, and aims to provide a preparation method of a lithium ion battery negative plate and application of the lithium ion battery negative plate in a lithium ion battery. Comprising the following steps: mixing the graphite anode material subjected to acidification treatment with CMC glue solution and a cross-linking agent to obtain anode slurry; coating the slurry on the surface of a current collector to enable the slurry to undergo esterification reaction and cross-linking to form gel; then placing the mixture in an asymmetric cold source for ultra-low temperature rapid freezing treatment; then vacuumizing to sublimate ice crystals in the gel to obtain a negative electrode material with a three-dimensional network structure and directional pore channels; and (3) performing heating treatment to carbonize the lithium ion battery negative plate, and finally obtaining the lithium ion battery negative plate with the three-dimensional conductive network. The low-tortuosity thick electrode with a regular three-dimensional straight-through pore canal is formed in the ice crystal sublimation process, so that the ion transmission characteristic of the thick electrode can be improved; the three-dimensional conductive network is uniformly distributed in the electrode, so that the mechanical strength can be improved, a good electronic conduction network is provided, and the battery has high energy density and high power density.

Description

Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery
Technical Field
The invention relates to a preparation method of a lithium ion battery negative plate and application of the lithium ion battery negative plate in a lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
In recent years, anxiety in endurance mileage places higher demands on the energy density of lithium ion batteries. At present, the preparation of ultra-thick electrodes with high coating weight is one of the most direct methods for improving specific energy of the battery. The construction of the thick electrode can reduce the content of inactive substances in the battery device layer, improve the energy density of the battery and reduce the cost of the battery. In addition, the structure of the thick electrode has universality and can be applied to various electrode materials.
The electrochemical performance of thick electrodes is mainly determined by Li in porous electrodes + Transmission control, li of electrode in charge-discharge process + Poor diffusion kinetics, forming a concentration gradient inside the electrode, resulting in increased concentration polarization; with the increase of the thickness, the substances inside the electrode have the problems of uneven distribution and uneven electrochemical reaction. In addition, as the thickness of the electrode increases, the increase in binder content in the paste may further bring about instability of the electrode, such as an increase in insulation. The thick electrode also has the crack of the pole piece, and the active substance and the current collector are separated from Li + And the like.
Thus, the microstructure of the thick electrode is designed and optimized to build efficient Li + The realization of the rapid charge and discharge of the battery is particularly important due to the transmission channel and the good electronic conduction network.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a lithium ion battery negative plate and application of the lithium ion battery negative plate in a lithium ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the lithium ion battery negative plate comprises the following steps:
(1) Weighing graphite cathode material and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5; adding sodium carboxymethylcellulose and a proper amount of deionized water into a high-speed refiner, and performing dispersion treatment to obtain CMC glue solution;
(2) Acidizing the graphite cathode by adopting mixed strong acid to ensure that the surface of the graphite cathode has hydrophilic function;
(3) Adding the graphite anode material subjected to acidification treatment and a proper amount of deionized water into CMC glue solution, and uniformly mixing; continuously adding carboxylic acid cross-linking agent, wherein the mass ratio of the cross-linking agent to CMC is 0.8:1; stirring continuously for 2 hours at room temperature to enable the cross-linking agent to be completely dispersed and dissolved, adding deionized water to adjust the viscosity to 4000-8000 mPa.s, and obtaining the cathode slurry with the solid content of 55-75%;
(4) Transferring the negative electrode slurry into a die with a current collector at the bottom, and adjusting the coating thickness according to the design requirement of an electrode; transferring the mould into a vacuum drying oven, and pre-drying at 60 ℃ to enable the slurry to undergo esterification reaction and cross-linking to form gel;
(5) Placing the die in an asymmetric cold source with a temperature difference of-150 ℃ to-90 ℃ to perform ultralow-temperature quick freezing treatment on the gel for 0.5-2 h; the CMC and graphite cathode materials are accumulated on two sides of the ice crystal body under the drive of ice crystal growth by utilizing the unidirectional condensation phenomenon of solvent water in gel under the asymmetric cold source condition; then vacuumizing to 1Pa for 8 hours to sublimate ice crystals in the gel, so as to obtain a negative electrode material with a three-dimensional network structure and directional pore channels;
(6) And (3) heating the cathode material by using a microwave heating device to carbonize the cathode material, and finally obtaining the lithium ion battery cathode plate with the three-dimensional conductive network.
In a preferred embodiment of the present invention, in the step (1), the graphite negative electrode material is artificial graphite.
As a preferable scheme of the invention, in the step (1), the rotating speed of the high-speed refiner is 3000-5000 rad/min during the dispersion treatment; the mass concentration of the CMC glue solution is 2-6%.
In the step (2), sulfuric acid and nitric acid are used for preparing a strong acid solution, and the pH value is 0.5-2; adding graphite cathode material, and acidizing at room temperature for 5-10 h; and (3) carrying out vacuum drying on the centrifugally separated solid to obtain the graphite anode material subjected to acidification treatment.
In a preferred embodiment of the present invention, in the step (3), the carboxylic acid-based crosslinking agent is citric acid.
In the step (4), the coating thickness is 100-800 μm; the pre-drying time was 4h.
In the preferred embodiment of the present invention, in the step (6), the power is 100 to 300W and the time is 1 to 10min when the heating treatment is performed by the microwave heating device.
The invention further provides an application of the negative plate in assembling a lithium ion battery based on the lithium ion battery negative plate prepared by the method.
Description of the inventive principles:
the invention prepares the negative electrode slurry by uniformly mixing a binder sodium carboxymethyl cellulose (CMC) with a graphite negative electrode material and adding a carboxylic acid cross-linking agent. Then, the prepared negative electrode slurry was coated on the surface of a current collector copper foil. Finally, constructing a thick electrode of the three-dimensional network channel with high conductivity without adhesive by using the ultralow temperature freezing effect to assist microwave heating.
The structure shortens the ion and electron migration path and provides a multidimensional open permeation channel; exhibiting low concentration polarization and rapid Li + And the transmission dynamics form a molecular-grade channel which is beneficial to lithium ion transportation, promote the high-speed conduction of lithium ions and facilitate the acquisition of excellent rapid charge and discharge capability.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. sodium carboxymethylcellulose (CMC) has more hydroxyl groups (-OH) on the molecular chain, and the carboxylic acid cross-linking agent generally has more than two carboxyl groups (-COOH) which are favorable for realizing full cross-linking. In the crosslinking process, the hydroxyl and carboxyl can generate esterification reaction to carry out dehydration condensation, so that the carboxyl and the CMC molecular chain are combined into a three-dimensional network structure. The low tortuosity thick electrode with regular three-dimensional through pore channels is formed in the ice crystal sublimation process by utilizing ultra-low temperature freeze drying, the orderly arranged through pore channels extend to the surface of a current collector, and the electrode can be used as a highway for lithium ion transmission, and the ion transmission characteristic of the thick electrode is improved. The three-dimensional conductive network formed by the high-pulse microwave heating technology is further uniformly distributed in the electrode, so that the mechanical strength of the electrode is improved, and a good electronic conduction network is provided.
2. The graphite negative electrode is acid treated to form oxygen-containing functional groups such as-CO, -COOH and the like on the surface of the graphite, particularly in the area (cracks and the like) with uneven surface, and the functional groups are Li + The lithium carboxylate is formed during the first insertion, which is favorable for forming the SEI film with stable structure, reduces the capacity loss caused by SEI film damage and repair in the material circulation process, and improves the circulation performance of the material. Meanwhile, the acid oxidation can remove part of defect structures in the graphite cathode, so that nano micropores are formed. These micropores are Li + Provides a new lithium storage site and improves the first charge and discharge capacity of the material. In addition, when the oxidized PH value is reduced to a certain degree, peroxidation occurs, more oxygen-containing functional groups are formed on the surface of graphite, and meanwhile strong acid has a certain corrosion effect on the surface of a graphite cathode, so that the electrochemical performance of the material is reduced. Therefore, the oxidation treatment using a strong acid solution having a pH of 1.0 has better electrochemical properties.
3. After the graphite negative electrode is subjected to acid treatment, the surface of the graphite negative electrode is provided with hydrophilic functional groups such as carboxyl and the like, the hydrophilic capacity of the graphite negative electrode can be changed, so that the graphite negative electrode can be stably dispersed in water for a long time. Meanwhile, the-OH functional group in CMC can be crosslinked with-COOH phase on graphite negative electrode material to form stable composite material with better dispersibility. The graphite anode material can be in-situ attached to a three-dimensional network structure in the crosslinking process of CMC and carboxylic acid cross-linking agents. In addition, the weak acidity of the carboxylic acid cross-linking agent can etch the surface of the copper foil to form uniform and rich open pits, so that the adhesion between the dressing layer and the copper foil is enhanced.
4. Conventional commercial binders PVDF, SBR, CMC, etc., fail to accommodate the volume change of the active material during the battery cycle due to lack of elasticity and toughness, which can lead to cracking of the active material, affect the capacity retention in the cycle and battery life, and these materials themselves can swell in the electrolyte, affecting the bond strength. The invention has the following advantages over commercial adhesives: (1) Adopting a three-dimensional network structure formed by a traditional adhesive CMC and a carboxylic acid cross-linking agent, and forming a thin conductive network on the surface of a graphite negative electrode in situ under the actions of low-temperature freezing and microwave field, so that the thick electrode does not contain the adhesive, and the performance attenuation caused by a large amount of adhesive in the thick electrode is reduced; (2) In the preparation process of the lithium ion battery electrode, no additional conductive agent is needed, a three-dimensional conductive network is formed in situ to serve as the conductive agent, the transmission path of ions and electrons is shortened, and the rapid charge and discharge capability of the thick electrode can be effectively improved; (3) The formed three-dimensional conductive network can provide a buffer space for the active material generated by expansion in the charge and discharge process, so that the cracking of the electrode plate is inhibited; (4) In the preparation process of the lithium ion battery electrode, the conductive agent is not added, so that the duty ratio of the active substance graphite cathode is improved, and the utilization rate of the thick electrode active substance is improved.
5. Although the thick electrode of the directional pore structure effectively solves the problem of the blocking of lithium ion transmission in the thick electrode, the high porosity caused by the directional pore structure also sacrifices the volume energy density of the battery. However, as the freezing temperature increases and the time increases, the diameter of the prepared three-dimensional network structure skeleton particles gradually increases, and the pores between the particles increase. Therefore, the invention prepares high solid content slurry (the solid content is confirmed to be about 65% by a plurality of tests and verification), reduces the ratio of solvent water, and simultaneously adopts the ultralow temperature rapid freezing effect to gradually reduce the diameter of the three-dimensional network structure skeleton particles, so that the pores among the particles are reduced. The three-dimensional network structure skeleton is quickly and fully carbonized by further adopting the high-pulse microwave heating effect, and the main graphite cathode material is not influenced.
6. The three-dimensional conductive network channel constructed by the invention effectively promotes the transmission of lithium ions and electrons in the electrode, accelerates the reaction kinetics of the thick electrode, reduces ohmic polarization and concentration polarization, and improves the rate capability and the problem of blocked transmission of cyclical stability. Meanwhile, a multidimensional open permeation channel is provided, so that rapid infiltration of electrolyte from the surface of the dressing layer to the current collector direction is facilitated, and the thick electrode battery has high energy density and high power density.
Drawings
Fig. 1 is an SEM image of the three-dimensional conductive network structure in example 1.
Fig. 2 is a graph showing the comparison of the rate charge/discharge performance of each example and comparative example.
Detailed Description
The invention constructs the thick electrode without adhesive and with the three-dimensional conductive network channel through the ultralow temperature freezing effect and the high pulse microwave effect, effectively solves the problems that the lithium ion transmission channel and the electronic conductive network cannot construct the electrolyte of the thick electrode, the wettability is poor, the electrode is cracked and the like, and realizes the comprehensive improvement of the high-rate charge and discharge performance and the stability of the thick electrode.
The invention specifically prepares a lithium ion battery negative plate by the following method, which comprises the following steps:
(1) Weighing graphite cathode material and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5; adding sodium carboxymethylcellulose and a proper amount of deionized water into a high-speed refiner, and performing dispersion treatment to obtain CMC glue solution; the rotating speed of the high-speed homogenizer is 3000-5000 rad/min during the dispersion treatment; the mass concentration of the CMC glue solution is 2-6%.
In the invention, the graphite cathode material adopts conventional artificial graphite, the production process of the material is mature, and a plurality of commercial products are available. The present invention is not particularly limited as long as it can be used for lithium ion batteries.
(2) Acidifying artificial graphite with mixed strong acid to make its surface possess hydrophilic function;
(3) Adding the acidified artificial graphite and part of deionized water into CMC glue solution, and uniformly mixing; continuously adding carboxylic acid cross-linking agent citric acid, wherein the mass ratio of the cross-linking agent to CMC is 0.8:1; stirring continuously for 2 hours at room temperature to enable the cross-linking agent to be completely dispersed and dissolved; adding deionized water to adjust the viscosity to 4000-8000 mPa.s to obtain the negative electrode slurry with the solid content of 55% -75%;
as an example, a strong acid solution with a pH of 0.5 to 2 is prepared with sulfuric acid and nitric acid; adding artificial graphite, and acidizing at room temperature for 5-10 h; and (3) carrying out vacuum drying on the centrifugally separated solid to obtain the graphite anode material subjected to acidification treatment.
(4) Transferring the negative electrode slurry into a die with a current collector at the bottom, and adjusting the coating thickness to be 100-800 mu m according to the design requirement of an electrode; transferring the mould into a vacuum drying oven, and pre-drying for 4 hours at 60 ℃ to enable the slurry to undergo esterification reaction and cross-linking to form gel;
(5) Placing the die in an asymmetric cold source with a temperature difference of-150 ℃ to-90 ℃ to perform ultralow-temperature quick freezing treatment on the gel for 0.5-2 h; the unidirectional condensation phenomenon of solvent water in gel under the asymmetric cold source condition is utilized to enable CMC and artificial graphite to be accumulated on two sides of the ice crystal body under the drive of ice crystal growth; then vacuumizing to 1Pa for 8 hours to sublimate ice crystals in the gel, so as to obtain a negative electrode material with a three-dimensional network structure and directional pore channels;
(6) And (3) heating the cathode material by using a microwave heating device to carbonize the cathode material, wherein the power is 100-300W, and the time is 1-10 min. Finally, the lithium ion battery negative plate with the three-dimensional conductive network is obtained.
The lithium ion battery negative plate prepared by the method can be further applied to a lithium ion battery, and particularly can be used as a battery negative electrode material for assembling the lithium ion battery. Because the negative plate is subjected to microwave heating treatment in the final treatment stage, the aerogel contained in the negative plate forms a three-dimensional network channel with high conductivity after carbonization; the structure shortens the ion and electron migration path and provides a multidimensional open permeation channel; exhibiting low concentration polarization and rapid Li + And the transmission dynamics form a molecular-grade channel which is beneficial to lithium ion transportation, promote the high-speed conduction of lithium ions and facilitate the acquisition of excellent rapid charge and discharge capability.
In order to better explain the above technical solution, the following describes the above technical solution in detail with reference to specific embodiments. It should not be construed that the scope of the above subject matter of the present invention is limited to the following embodiments, and all techniques implemented based on the above description of the present invention are within the scope of the present invention.
Example 1
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at a high speed dispersion speed of 4000rad/min to prepare a CMC gum solution having a mass concentration of 4.6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-120 ℃ for 1h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S6: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S5 by adopting a high-pulse microwave heating device with heating power of 200W for 5min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Example 2
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 128.87g deionized water were transferred to an ultra high speed refiner and high speed dispersion was performed at 3000rad/min to prepare CMC gum solution at a concentration of 2.0%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution with pH of 0.5 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, carrying out acidification treatment on 50g of artificial graphite at room temperature for 5 hours, and obtaining the oxidized graphite anode material through centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 4000 mPas to obtain the cathode slurry with the solid content of 55%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed on the bottom, and the coating thickness was adjusted to 100 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-150 ℃ for 0.5h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S6: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S5 by adopting a high-pulse microwave heating device with heating power of 100W for 1min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Example 3
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 41.20g deionized water were transferred to an ultra high speed refiner at a speed of 5000rad/min to prepare a CMC dope with a concentration of 6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution with pH of 2.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 10 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 8000 mPas to obtain the negative electrode slurry with the solid content of 75%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 800 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-90 ℃ for 2 hours to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S6: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S5 by adopting a high-pulse microwave heating device with heating power of 300W for 10min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Comparative example 1 (without carboxylic acid cross-linker)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 4.6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: and (3) adding the product prepared in the step (S2) and deionized water into the CMC glue solution in the step (S1) to prepare the negative electrode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step S4 at the low temperature of-120 ℃ for 1h. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Comparative example 2 (graphite negative electrode was not acid-treated)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 4.6%.
Step S2: adding 50g of artificial graphite and deionized water into the CMC glue solution in the step S1 to prepare electrode slurry, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S3: the negative electrode slurry in step S2 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S4: and (3) rapidly freezing the die in the step (S3) at the low temperature of-120 ℃ for 1h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S5: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S4 by adopting a high-pulse microwave heating device with heating power of 200W for 5min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Comparative example 3 (no preparation of high concentration CMC dope)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 260.37g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 1%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into CMC glue solution in the step S1 to prepare electrode slurry with the solid content of 65%, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-120 ℃ for 1h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S6: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S5 by adopting a high-pulse microwave heating device with heating power of 200W for 5min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Comparative example 4 (no high solids slurry was prepared)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 4.6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-120 ℃ for 1h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Step S6: and (3) rapidly carbonizing the three-dimensional network structure in the thick electrode in the step S5 by adopting a high-pulse microwave heating device with heating power of 200W for 5min, so as to obtain the thick electrode without adhesive and provided with the three-dimensional conductive network.
Comparative example 5 (ultra low temperature freezing effect but no high pulse microwave heating)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 4.6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. And transferring the mould into a vacuum drying oven, and rapidly predrying for 4 hours at 60 ℃ to crosslink and shape the slurry.
Step S5: and (3) rapidly freezing the die in the step (S4) at the low temperature of-120 ℃ for 1h to fix gel formed by CMC and carboxylic acid cross-linking agent in the esterification reaction process. Because solvent water has the phenomenon of unidirectional condensation under an asymmetric cold source, an ice crystal structure can be formed on the cold side and can grow along a temperature gradient, after the mixed solution of CMC and artificial graphite and deionized water is cooled on one side, CMC and artificial graphite can be accumulated on two sides of an ice crystal body under the drive of ice crystal growth. And then vacuumizing to 1Pa for 8 hours, so that the ice crystals sublimate, through holes with a three-dimensional network structure are formed at the original ice crystal positions, and the material with the directional pore channel structure can promote lithium ion transmission in the thick electrode, so that the electrochemical performance of the thick electrode battery is improved.
Comparative example 6 (no ultralow temperature freezing effect and no high pulse microwave heating)
Step S1: weighing artificial graphite and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5.
2.63g CMC and 54.54g deionized water were transferred to an ultra high speed refiner at 4000rad/min to prepare a CMC dope with a concentration of 4.6%.
Step S2: and (3) carrying out functionalization treatment on the artificial graphite by adopting mixed strong acid to ensure that the surface of the artificial graphite has hydrophilic function. A strong acid solution having a pH of 1.0 was prepared at a volume ratio of sulfuric acid to nitric acid of 3:1. And then, 50g of artificial graphite is acidized for 8 hours at room temperature, and the graphite anode material subjected to oxidation treatment is obtained after centrifugation and vacuum drying.
Step S3: adding the product prepared in the step S2 and deionized water into the CMC glue solution in the step S1, uniformly mixing, adding 2.10g of citric acid, and continuously stirring at room temperature for 2 hours to completely disperse and dissolve the crosslinking agent; adding deionized water to adjust the viscosity of the slurry to 6000 mPa.s, and obtaining the cathode slurry with the solid content of 65%.
Step S4: the negative electrode slurry in step S3 was transferred to a die with a current collector copper foil placed at the bottom, and the coating thickness was adjusted to 300 μm with a doctor blade. The mold was then transferred to a vacuum oven and dried at 80℃for 12h.
Product performance test:
and (3) preparing an electrode before electrochemical testing, assembling the button cell, and testing the electrical performance of the cell by adopting a charge-discharge testing cabinet.
The lithium ion battery negative plate prepared by the embodiment 1 of the invention has good multiplying power and good cycle stability.
As can be clearly seen from the SEM of fig. 1, the three-dimensional conductive network structure has a three-dimensional cross-linked and intercommunicated wall layer structure with thinner wall layers and tightly stacked together, the adjacent wall layers share the same wall layer, and the protruding transverse rib structure inside the hole is beneficial to enhancing the mechanical strength.
As can be seen from the electrical performance test results of fig. 2, the negative electrode sheet prepared in example 1 has better rate performance and capacity recovery performance.
According to analysis examples and comparative examples 1-6, it can be obtained that the microstructure properties of the thick electrode can be regulated and controlled by controlling key factors such as acid treatment of the graphite anode, addition of carboxylic acid cross-linking agent, ultra-low temperature drying, high pulse microwave heating and the like, and high-efficiency Li can be constructed + And the transmission channel and a good electron conduction network realize the rapid charge and discharge capability of the thick electrode. In the embodiment 1 of the invention, the coupling effect of different functions is realized by adopting the three-dimensional conductive network structure design constructed by graphite negative electrode acid treatment @ adding carboxylic acid cross-linking agent @ ultralow temperature drying @ high pulse microwave heating: the structure not only reduces the cost of materials, but also realizes the comprehensive improvement of the high-rate charge-discharge performance and stability of the thick electrode. In contrast, the electrochemical performance of thick electrodes is not well improved by using a single material structure or by the lack of a certain material structure (comparative examples 1-6) and by using certain critical parameters improperly in the preparation process (examples 2-3).
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.

Claims (9)

1. The preparation method of the lithium ion battery negative plate is characterized by comprising the following steps of:
(1) Weighing graphite cathode material and sodium carboxymethylcellulose (CMC) serving as a binder according to a mass ratio of 95:5;
adding sodium carboxymethylcellulose and a proper amount of deionized water into a high-speed refiner, and performing dispersion treatment to obtain CMC glue solution;
(2) Acidizing the graphite cathode by adopting mixed strong acid to ensure that the surface of the graphite cathode has hydrophilic function;
(3) Adding the graphite anode material subjected to acidification treatment and a proper amount of deionized water into CMC glue solution, and uniformly mixing; continuously adding carboxylic acid cross-linking agent, wherein the mass ratio of the cross-linking agent to CMC is 0.8:1; stirring continuously for 2 hours at room temperature to enable the cross-linking agent to be completely dispersed and dissolved, adding deionized water to adjust the viscosity to 4000-8000 mPa.s, and obtaining the cathode slurry with the solid content of 55-75%;
(4) Transferring the negative electrode slurry into a die with a current collector at the bottom, and adjusting the coating thickness according to the design requirement of an electrode; transferring the mould into a vacuum drying oven, and pre-drying at 60 ℃ to enable the slurry to undergo esterification reaction and cross-linking to form gel;
(5) Placing the die in an asymmetric cold source with a temperature difference of-150 ℃ to-90 ℃ to perform ultralow-temperature quick freezing treatment on the gel for 0.5-2 h; the CMC and graphite cathode materials are accumulated on two sides of the ice crystal body under the drive of ice crystal growth by utilizing the unidirectional condensation phenomenon of solvent water in gel under the asymmetric cold source condition; then vacuumizing to 1Pa for 8 hours to sublimate ice crystals in the gel, so as to obtain a negative electrode material with a three-dimensional network structure and directional pore channels;
(6) And (3) heating the cathode material by using a microwave heating device to carbonize the cathode material, and finally obtaining the lithium ion battery cathode plate with the three-dimensional conductive network.
2. The method of claim 1, wherein in step (1), the graphite negative electrode material is artificial graphite.
3. The method according to claim 1, wherein in the step (1), the rotation speed of the high-speed refiner during the dispersion treatment is 3000 to 5000rad/min; the mass concentration of the CMC glue solution is 2-6%.
4. The method according to claim 1, wherein in the step (2), a strong acid solution is prepared by sulfuric acid and nitric acid, and the pH value is 0.5-2; adding graphite cathode material, and acidizing at room temperature for 5-10 h; and (3) carrying out vacuum drying on the centrifugally separated solid to obtain the graphite anode material subjected to acidification treatment.
5. The method of claim 1, wherein in step (3), the carboxylic acid-based cross-linking agent is citric acid.
6. The method according to claim 1, wherein in the step (4), the coating thickness is 100 to 800 μm; the pre-drying time was 4h.
7. The method according to claim 1, wherein in the step (6), the power is 100 to 300W and the time is 1 to 10min when the heating treatment is performed by the microwave heating device.
8. The lithium ion battery negative plate prepared by the method according to any one of claims 1 to 7.
9. The use of the lithium ion battery negative electrode sheet of claim 8 in assembling a lithium ion battery.
CN202311631560.2A 2023-12-01 2023-12-01 Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery Pending CN117613201A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311631560.2A CN117613201A (en) 2023-12-01 2023-12-01 Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311631560.2A CN117613201A (en) 2023-12-01 2023-12-01 Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery

Publications (1)

Publication Number Publication Date
CN117613201A true CN117613201A (en) 2024-02-27

Family

ID=89949572

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311631560.2A Pending CN117613201A (en) 2023-12-01 2023-12-01 Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery

Country Status (1)

Country Link
CN (1) CN117613201A (en)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150228968A1 (en) * 2014-02-11 2015-08-13 Battelle Memorial Institute Thick Electrodes Including Nanoparticles Having Electroactive Materials and Methods of Making Same
WO2018176063A2 (en) * 2017-03-15 2018-09-27 Research Foundation Of The City University Of New York A stabilized birnessite cathode for high power and high energy density applications
CN108878886A (en) * 2018-07-10 2018-11-23 东莞市迈科新能源有限公司 A kind of battery thickness pole piece and its water base compound binding agent
CN111564639A (en) * 2020-05-28 2020-08-21 贝特瑞新材料集团股份有限公司 Lithium ion battery pole piece, preparation method and application thereof
CN114361409A (en) * 2021-12-02 2022-04-15 华中科技大学 Method for improving high-voltage long-cycle performance of layered positive electrode material at thick electrode
CN114400301A (en) * 2022-03-09 2022-04-26 中南大学 High-performance thick pole piece of lithium ion battery and preparation method thereof
CN114744200A (en) * 2022-05-11 2022-07-12 湘潭大学 Ionic crosslinked polymer, conductive adhesive, and preparation method and application thereof
CN114976030A (en) * 2022-04-14 2022-08-30 双登集团股份有限公司 Lithium ion battery for energy storage and preparation method thereof
CN115224243A (en) * 2022-06-13 2022-10-21 河南师范大学 Preparation method of lithium ion battery negative plate
US20220376256A1 (en) * 2020-02-21 2022-11-24 Shanghai Jiao Tong University Flexible multifunctional cross-linking adhesive, preparation method therefor and application thereof
CN115692615A (en) * 2021-07-30 2023-02-03 华中科技大学 Low-tortuosity thick electrode based on aqueous binder, and preparation and application thereof
CN115692593A (en) * 2021-07-30 2023-02-03 华中科技大学 Sulfur anode with layered reinforced concrete structure and preparation and application thereof
CN115832311A (en) * 2022-12-29 2023-03-21 重庆硕盈峰新能源科技有限公司 Lithium ion battery negative electrode binder, slurry, negative electrode plate and lithium battery
CN117096270A (en) * 2023-08-29 2023-11-21 合肥国轩高科动力能源有限公司 Double-layer porous structure silicon-based thick electrode of lithium ion battery and preparation method and application thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150228968A1 (en) * 2014-02-11 2015-08-13 Battelle Memorial Institute Thick Electrodes Including Nanoparticles Having Electroactive Materials and Methods of Making Same
WO2018176063A2 (en) * 2017-03-15 2018-09-27 Research Foundation Of The City University Of New York A stabilized birnessite cathode for high power and high energy density applications
CN108878886A (en) * 2018-07-10 2018-11-23 东莞市迈科新能源有限公司 A kind of battery thickness pole piece and its water base compound binding agent
US20220376256A1 (en) * 2020-02-21 2022-11-24 Shanghai Jiao Tong University Flexible multifunctional cross-linking adhesive, preparation method therefor and application thereof
CN111564639A (en) * 2020-05-28 2020-08-21 贝特瑞新材料集团股份有限公司 Lithium ion battery pole piece, preparation method and application thereof
CN115692615A (en) * 2021-07-30 2023-02-03 华中科技大学 Low-tortuosity thick electrode based on aqueous binder, and preparation and application thereof
CN115692593A (en) * 2021-07-30 2023-02-03 华中科技大学 Sulfur anode with layered reinforced concrete structure and preparation and application thereof
CN114361409A (en) * 2021-12-02 2022-04-15 华中科技大学 Method for improving high-voltage long-cycle performance of layered positive electrode material at thick electrode
CN114400301A (en) * 2022-03-09 2022-04-26 中南大学 High-performance thick pole piece of lithium ion battery and preparation method thereof
CN114976030A (en) * 2022-04-14 2022-08-30 双登集团股份有限公司 Lithium ion battery for energy storage and preparation method thereof
CN114744200A (en) * 2022-05-11 2022-07-12 湘潭大学 Ionic crosslinked polymer, conductive adhesive, and preparation method and application thereof
CN115224243A (en) * 2022-06-13 2022-10-21 河南师范大学 Preparation method of lithium ion battery negative plate
CN115832311A (en) * 2022-12-29 2023-03-21 重庆硕盈峰新能源科技有限公司 Lithium ion battery negative electrode binder, slurry, negative electrode plate and lithium battery
CN117096270A (en) * 2023-08-29 2023-11-21 合肥国轩高科动力能源有限公司 Double-layer porous structure silicon-based thick electrode of lithium ion battery and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JING WANG等: ""Scalable Preparation of Ternary Hierarchical Silicon Oxide– Nickel–Graphite Composites for Lithium-Ion Batteries"", 《CHEMSUSCHEM》, vol. 8, 9 November 2015 (2015-11-09), pages 4073 - 4080 *
刘丹丹等: ""锂浆料电池基础科学问题研究"", 《化学进展》, vol. 30, no. 06, 24 June 2018 (2018-06-24), pages 765 - 774 *
杨续来等: ""高能量密度锂离子电池结构工程化技术探讨"", 《储能科学与技术》, vol. 9, no. 04, 3 June 2020 (2020-06-03), pages 1127 - 1136 *
熊 鹏: ""高粘度羧甲基纤维素钠合成工艺及其在硅负极中应用研究"", 《中国优秀硕士学位论文全文数据库(电子期刊)》, 15 January 2018 (2018-01-15), pages 016 - 99 *

Similar Documents

Publication Publication Date Title
CN110148708B (en) Negative plate and lithium ion battery
CN111725504B (en) Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN112117434B (en) High-capacity electrode of solid sodium battery and preparation method and application thereof
CN112670507A (en) Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery
CN114400301A (en) High-performance thick pole piece of lithium ion battery and preparation method thereof
CN111048781A (en) High-compaction-resistant composite conductive agent and application thereof in lithium ion battery
Xiong et al. SiO x-based graphite composite anode and efficient binders: practical applications in lithium-ion batteries
CN108461691A (en) A kind of lithium-sulfur cell diaphragm and preparation method thereof
CN116741973B (en) Graphene-like coated silicon-carbon nanotube composite material and preparation method and application thereof
CN115692593A (en) Sulfur anode with layered reinforced concrete structure and preparation and application thereof
CN116477599B (en) Hard carbon negative electrode material and preparation method and application thereof
CN109921098B (en) Preparation method of water system super nano lithium iron phosphate battery
CN117613201A (en) Preparation method of lithium ion battery negative plate and application of lithium ion battery negative plate in lithium ion battery
CN108461755B (en) Lithium metal battery negative electrode framework material and preparation method thereof and lithium metal battery negative electrode
CN115312777A (en) Low-tortuosity thick electrode and preparation method and application thereof
CN115304052A (en) Wood-based composite hard carbon negative electrode material and preparation method and application thereof
CN114388745A (en) High-performance lithium ion battery self-supporting polymer thick pole piece and preparation method thereof
CN114342105A (en) Preparation method of composite cathode of lithium ion battery
CN115692623B (en) Lithium ion battery negative plate, preparation method thereof and lithium ion battery
CN115020914B (en) Cattail-structured ceramic composite diaphragm interlayer for lithium/sodium-sulfur battery and preparation method thereof
CN115224238B (en) Lithium ion battery negative pole piece, manufacturing method thereof and laser carbonization device
CN1956245A (en) Negative pole active material and lithium ion battery using the material and its preparation method
CN117038946A (en) Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery
CN115411224A (en) Solid-state battery with electrode plate of lithium battery with ultralow porosity
CN115425175A (en) Thick electrode and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination