CN108470909B - Crosslinked network composite adhesive, application thereof, lithium ion battery cathode material prepared based on crosslinked network composite adhesive and preparation method of lithium ion battery cathode material - Google Patents
Crosslinked network composite adhesive, application thereof, lithium ion battery cathode material prepared based on crosslinked network composite adhesive and preparation method of lithium ion battery cathode material Download PDFInfo
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- CN108470909B CN108470909B CN201810205056.9A CN201810205056A CN108470909B CN 108470909 B CN108470909 B CN 108470909B CN 201810205056 A CN201810205056 A CN 201810205056A CN 108470909 B CN108470909 B CN 108470909B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a cross-linked network composite adhesive, application thereof, a lithium ion battery cathode material prepared based on the cross-linked network composite adhesive and a preparation method of the lithium ion battery cathode material, and belongs to the technical field of electrochemistry and new energy materials. The cross-linked network composite adhesive is formed by cross-linking sodium carboxymethylcellulose and fulvic acid through glutaraldehyde. The lithium ion battery cathode slurry applying the cross-linked network composite adhesive consists of an active material, a conductive agent and a binder. The cross-linking type composite binder can form a cross-linking network structure, and the cross-linking network binder can perform multi-dimensional hydrogen bond interaction with silicon particles, so that the binding property is enhanced, the mechanical property is improved, the complete structure of an electrode is kept, and the cycle performance of a battery is improved. The cross-linking type composite binder has wide raw material sources and is a green and environment-friendly composite binder.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and new energy materials, and particularly relates to a cross-linked network composite adhesive, application thereof, a lithium ion battery cathode material prepared based on the cross-linked network composite adhesive and a preparation method of the lithium ion battery cathode material.
Background
At present, lithium ion batteries have been successfully applied to portable electronic devices such as mobile phones and notebooks, and have gradually developed into various fields such as aerospace, electric vehicles and energy storage systems. The new application provides higher requirements for the performances of the lithium ion battery, such as specific capacity, rate characteristic, cycle life and the like. The silicon material has the theoretical specific capacity up to 4200mAh/g, has lower lithium intercalation/deintercalation potential and good safety performance, and is expected to become a new generation of cathode material. However, in the charge and discharge cycle process of the silicon material, along with the insertion and extraction of lithium ions, the high-specific-capacity negative electrode repeatedly undergoes huge volume change, is easy to pulverize and strip, and the electrode structure is seriously damaged, so that the cycle specific capacity of the silicon material is rapidly reduced, and the practical application of the silicon material in the lithium ion battery is limited.
The lithium ion battery has the advantages of high capacity, long service life, more cycle times, no memory effect, less self-discharge, environmental protection, wide use temperature range, high rate, safety and the like, and is widely applied to mobile phones, computers, electric bicycles, electric automobiles and the like. The volume expansion of the positive pole piece and the negative pole piece of the battery in the charging and discharging process can affect the performance of the lithium ion battery.
At present, the reduction of the expansion rate of a pole piece is one of the hot points of research, the development of a low-expansion graphite negative electrode is urgent, and a binder is an effective means for solving the expansion of the graphite negative electrode. The strong cohesive force of the macromolecular structure of the adhesive can effectively inhibit the expansion effect of the pole piece, so that the adhesive has particularly remarkable effect in the development of low-expansion graphite. Meanwhile, the silicon-based material has the advantages of high capacity, good cycle performance, good multiplying power and the like, but the silicon-based material has large volume expansion in the charge-discharge process and is limited in application, and the silicon-based material can play a role in inhibiting expansion through a special high molecular structure of the binder. Therefore, the preparation of the adhesive which is low in dosage, strong in adhesive force and capable of effectively inhibiting the expansion of the pole piece, particularly the expansion of the graphite negative electrode and the silicon-based material, is not only a future development trend, but also an urgent need of the market.
Disclosure of Invention
The invention aims to provide a cross-linked network composite adhesive, application thereof, a lithium ion battery cathode material prepared based on the cross-linked network composite adhesive and a preparation method of the lithium ion battery cathode material.
The invention is realized by the following technical scheme:
the invention discloses a cross-linked network composite adhesive, which is formed by cross-linking sodium carboxymethylcellulose, fulvic acid and glutaraldehyde, and has the structural formula shown as the following formula:
wherein n is 50-100.
Preferably, the mass ratio of the sodium carboxymethylcellulose to the fulvic acid to the glutaraldehyde is (5-12): (1-3): (0.1-0.5).
Preferably, the mass ratio of the sodium carboxymethylcellulose to the fulvic acid to the glutaraldehyde is (5-10): (1-2): (0.1-0.3).
The invention also discloses a preparation method of the cross-linked network composite adhesive, which comprises the steps of mixing sodium carboxymethylcellulose, fulvic acid and glutaraldehyde, preparing an aqueous solution with the mass concentration of 0.5-2.0% by taking water as a dispersion system, and reacting the aqueous solution at 70 ℃ for 1 hour to prepare the cross-linked network composite adhesive.
The invention also discloses application of the cross-linked network composite adhesive in preparation of a lithium ion battery cathode material.
The invention also discloses a lithium ion battery cathode material, which comprises the following components in percentage by mass: 50-80% of active material, 10-30% of conductive agent and 10-20% of the cross-linked network composite adhesive.
Preferably, the active material adopts a silicon negative electrode, a graphite negative electrode or sulfide; the conductive agent adopts acetylene black or superconducting carbon black.
The invention also discloses a preparation method of the lithium ion battery cathode material, which comprises the following steps:
1) fully and uniformly grinding the active material and the conductive agent, then dropwise adding the cross-linked network composite adhesive aqueous solution, and continuously grinding until the cross-linked network composite adhesive is uniformly mixed in the active material and the conductive agent to prepare electrode slurry;
2) placing the product prepared in the step 1) on a Cu sheet and uniformly coating;
3) drying the Cu sheet treated in the step 2) to prepare a pole piece, and drying the pole piece in vacuum;
4) and weighing the pole piece slide glass after vacuum drying to obtain the lithium ion battery negative electrode material for assembling the battery.
Preferably, in the step 1), the active material and the conductive agent are fully ground for 5-10 min.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a cross-linked network composite adhesive, which is prepared by cross-linking sodium carboxymethyl cellulose and fulvic acid through glutaraldehyde, wherein a polar carboxyl group in sodium carboxymethyl cellulose can form a hydrogen bond action mechanism with self-repairing capability with an-OH group on the silicon surface, and the strong hydrogen bond action can be continuously broken and generated, so that the cross-linked network composite adhesive adapts to the volume change of silicon particles in the circulation process and keeps the structural integrity and the electric connectivity of an electrode. Fulvic acid is extracted from low-grade coal (peat, brown coal and weathered coal). The fulvic acid is composed of aromatic hydroxycarboxylic acid substances, and can enhance the binding power between the binding agent and the silicon particles through hydrogen bonds and the electrostatic attraction of a humic acid molecule dipole electric field, thereby effectively adapting to the huge volume change in the circulation process and further improving the circulation stability of the battery. The glutaraldehyde cross-linked sodium carboxymethylcellulose and the fulvic acid are adopted to form a cross-linked network structure, the cross-linked network binder can perform multi-dimensional hydrogen bond interaction with silicon particles, the cohesiveness is enhanced, the mechanical property is improved, the complete structure of an electrode is favorably maintained, the pulverization and the falling of the silicon particles are prevented in the charging and discharging processes, and the cycle performance of the battery is improved. The cross-linking type composite binder has wide raw material sources and is a novel green and environment-friendly composite binder. Therefore, the crosslinking composite binder can improve the cycle stability of the lithium ion battery negative electrode material and prolong the service life of the battery.
The lithium ion battery cathode material prepared based on the cross-linked network composite adhesive has better cycle stability and longer service life.
The preparation method of the lithium ion battery cathode material disclosed by the invention is simple to operate, has low requirements on equipment, and is easy for large-scale production.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention adopts the cross-linked network composite adhesive as the lithium ion battery cathode material adhesive. The structural formula is as follows:
wherein n is 50-100.
The cross-linked network composite adhesive is formed by cross-linking sodium carboxymethylcellulose, fulvic acid and glutaraldehyde;
dissolving sodium carboxymethylcellulose, fulvic acid and glutaraldehyde into a dispersion medium to form a solution with the concentration of 0.5-2.0 wt%, wherein the dispersion medium is deionized water, and the mass ratio of the sodium carboxymethylcellulose to the fulvic acid to the glutaraldehyde is (5-10): (1-2): (0.1-0.3).
The cross-linking type composite binder is usually prepared into 0.5-2.0 wt% of solution for preparing an electrode material of a lithium ion battery, and deionized water is used as a diluent to prepare the thickness of slurry in the preparation process.
The negative electrode material of the lithium ion battery comprises the following components in percentage by mass: conductive agent: the cross-linked network composite adhesive is (50-80): (10-30): (10-20).
The lithium ion battery negative electrode active material comprises a silicon negative electrode, a graphite negative electrode and a sulfide, and preferably a nano silicon negative electrode; the conductive agent adopts acetylene black or superconducting carbon black, and acetylene black is preferred. The preparation method comprises the steps of mixing the slurry for not less than 30 minutes, coating the film with the thickness of 100-200 mu m (preferably 100nm), and drying the film at the temperature of 60-80 ℃.
The preparation method of the silicon negative electrode material of the lithium ion battery comprises the following steps:
step 1: preparing a mixture of sodium carboxymethylcellulose, fulvic acid and glutaraldehyde into an aqueous solution with the mass concentration of 0.5-2.0 wt% according to a certain proportion, and reacting the aqueous solution at 70 ℃ for 1h to obtain the cross-linked composite binder. (ii) a
Step 2: grinding the active substance and the conductive agent in a mortar for 5-10 minutes;
and step 3: dropwise adding the crosslinking type composite binder prepared in the step 1 into the mixture obtained in the step 2, and grinding until the binder is uniformly mixed with the active substance and the conductive agent;
and 4, step 4: dropwise adding deionized water into the mixture obtained in the step 3, and then fully grinding for 20-30 minutes;
and 5: pouring the mixture obtained in the step (4) on a Cu sheet, and uniformly coating;
step 6: rapidly drying the copper sheet obtained in the step 5 by air blowing to remove solvent water to obtain a pole piece, and drying the pole piece in vacuum;
and 7: and weighing the vacuum-dried pole piece cut pieces, and assembling the battery.
The raw materials used in the invention are all commercial products, and the fulvic acid is purchased from Shandong Yousio chemical technology Co., Ltd, a product number of 059415001200.
Example 1
Firstly, 0.5 wt% of cross-linked network composite adhesive is prepared, wherein the mass ratio of the sodium carboxymethyl cellulose to the fulvic acid to the glutaraldehyde is 10:1:0.1, and the weight ratio is recorded as 10:1:0.1 of CMC/HA/GA. 60.0mg of nano Si and 30.0mg of acetylene black were weighed and put in a mortar, and ground for 10 minutes, and then 2.0g of a 0.5 wt% crosslinking type composite binder was dropped. Grinding for 5 minutes until the binder is uniformly mixed with the silicon powder and the carbon powder, then dripping 1mL of deionized water, and then fully grinding for 15-10 minutes. The pasty mixture was placed on a Cu sheet, uniformly coated with a 100 μm doctor blade, quickly placed in a forced air drying cabinet at 60 ℃ and taken out after five minutes. And then putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 6h at the constant temperature of 80 ℃. Weighing the vacuum-dried pole piece cut pieces, assembling the pole piece cut pieces in a glove box in a 2032 battery case, taking a lithium piece as a positive electrode, taking a polyethylene film as a diaphragm and taking 1mol/L LiPF6EC/DMC/DEC (v/v/v-1/1/1) was used for constant current charge and discharge test of the assembled battery.
Example 2
Firstly, preparing 1.0 wt% of cross-linked network composite adhesive, wherein the mass ratio of the sodium carboxymethylcellulose, the fulvic acid and the glutaraldehyde is 5:2:0.3, and the mass ratio is recorded as CMC/HA/GA being 5:2: 0.3. 80.0mg of nano Si and 10.0mg of acetylene black were weighed and put in a mortar, and ground for 10 minutes, and then 1.0g of 1.0 wt% of a crosslinking type composite binder was dropped. Grinding for 5 minutes until the binder is uniformly mixed with the Si powder and the carbon powder, then dripping 1mL of deionized water, and then fully grinding for 15-10 minutes. The pasty mixture was placed on a Cu sheet, uniformly coated with a 100 μm doctor blade, quickly placed in a forced air drying cabinet at 60 ℃ and taken out after five minutes. Then putting the pole piece into a vacuum drying ovenAnd (5) drying for 6 hours in vacuum at the constant temperature of 80 ℃. Weighing the vacuum-dried pole piece cut pieces, assembling the pole piece cut pieces in a glove box in a 2032 battery case, taking a lithium piece as a positive electrode, taking a polyethylene film as a diaphragm and taking 1mol/L LiPF6EC/DMC/DEC (v/v/v-1/1/1) was used for constant current charge and discharge test of the assembled battery.
Example 3
Firstly, preparing 2.0 wt% of cross-linked network composite adhesive, wherein the mass ratio of the sodium carboxymethylcellulose, the fulvic acid and the glutaraldehyde is 5:2:0.1, and the mass ratio is recorded as CMC/HA/GA being 5:2: 0.1. 50.0mg of nano Si and 30.0mg of acetylene black were weighed and put in a mortar, and ground for 10 minutes, and then 1.0g of a 2.0 wt% crosslinking type composite binder was dropped. Grinding for 5 minutes until the binder is uniformly mixed with the Si powder and the carbon powder, then dripping 1mL of deionized water, and then fully grinding for 15-10 minutes. The pasty mixture was poured onto a Cu sheet, uniformly coated with a 100 μm doctor blade, quickly placed in a forced air drying cabinet at 60 ℃ and taken out after five minutes. And then putting the pole piece into a vacuum drying oven, and carrying out vacuum drying for 6h at the constant temperature of 80 ℃. Weighing the vacuum-dried pole piece cut pieces, assembling the pole piece cut pieces in a glove box in a 2032 battery case, taking a lithium piece as a positive electrode, taking a polyethylene film as a diaphragm and taking 1mol/L LiPF6EC/DMC/DEC (v/v/v-1/1/1) was used for constant current charge and discharge test of the assembled battery.
Comparative example
In contrast to example 2, only sodium carboxymethylcellulose (CMC) was used as binder.
The electrochemical performance of the silicon negative electrode material of the crosslinking type composite binder provided by the invention is tested through charge-discharge cycles. Table 1 shows the cycle performance of the silicon electrodes of the examples of the present invention and the comparative examples at a charge/discharge current density of 100 mA/g.
TABLE 1
Table 1 shows the capacity and charge-discharge efficiency data of the corresponding examples. As can be seen from Table 1, the first discharge capacities of the crosslinking type composite binders are all higher than 3000 mAh/g. The first efficiency of CMC as binder was below 80%. At the 200 th cycle, the electrode discharge capacities of the CMC used as the binder were all lower than 100 mAh/g. And the discharge capacity of the cross-linked composite binder electrode is higher than 2000 mAh/g.
Claims (2)
1. The lithium ion battery negative electrode material is characterized by comprising the following components in percentage by mass: 50-80% of active material, 10-30% of conductive agent and 10-20% of cross-linked network composite adhesive;
the cross-linked network composite adhesive is formed by cross-linking sodium carboxymethylcellulose, fulvic acid and glutaraldehyde, and has the following structural formula:
wherein n is 50-100;
the mass ratio of the sodium carboxymethylcellulose to the fulvic acid to the glutaraldehyde is (5-10): (1-2): (0.1 to 0.3); mixing sodium carboxymethylcellulose, fulvic acid and glutaraldehyde, taking water as a dispersion system to prepare an aqueous solution with the mass concentration of 0.5-2.0%, and reacting the aqueous solution at 70 ℃ for 1h to prepare the cross-linked network composite adhesive;
the active material adopts a silicon cathode; the conductive agent adopts acetylene black or superconducting carbon black.
2. The preparation method of the lithium ion battery negative electrode material of claim 1, characterized by comprising the following steps:
1) fully and uniformly grinding the active material and the conductive agent, then dropwise adding the cross-linked network composite adhesive aqueous solution, and continuously grinding until the cross-linked network composite adhesive is uniformly mixed in the active material and the conductive agent to prepare electrode slurry; fully grinding the active material and the conductive agent for 5-10 min;
2) placing the product prepared in the step 1) on a Cu sheet and uniformly coating;
3) drying the Cu sheet treated in the step 2) to prepare a pole piece, and drying the pole piece in vacuum;
4) and weighing the pole piece slide glass after vacuum drying to obtain the lithium ion battery negative electrode material for assembling the battery.
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| CN201810205056.9A CN108470909B (en) | 2018-03-13 | 2018-03-13 | Crosslinked network composite adhesive, application thereof, lithium ion battery cathode material prepared based on crosslinked network composite adhesive and preparation method of lithium ion battery cathode material |
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| CN113363482B (en) * | 2021-04-25 | 2022-12-23 | 广东工业大学 | Composite binder for silicon-based negative electrode of lithium ion battery and preparation method and application thereof |
| WO2024007242A1 (en) * | 2022-07-07 | 2024-01-11 | 宁德时代新能源科技股份有限公司 | Binder, binder composition, preparation method, negative electrode slurry, negative electrode sheet, secondary battery, battery module, battery pack, and electric apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682031A (en) * | 2007-02-09 | 2010-03-24 | 原子能委员会 | Be used for the electrode of electrochemical system adhesive, comprise the electrode of this adhesive and comprise the electrochemical system of this electrode |
| CN105914376A (en) * | 2016-06-24 | 2016-08-31 | 辽宁九夷锂能股份有限公司 | Reinforced type composite binder for negative electrode of lithium ion battery and application of reinforced type composite binder |
| CN107359351A (en) * | 2017-06-29 | 2017-11-17 | 郑州大学 | A kind of method that lithium ion battery prepares electrode slice with humic acid base water-based binder and using the binding agent |
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| US10597389B2 (en) * | 2016-08-22 | 2020-03-24 | Global Graphene Group, Inc. | Humic acid-bonded metal foil film current collector and battery and supercapacitor containing same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682031A (en) * | 2007-02-09 | 2010-03-24 | 原子能委员会 | Be used for the electrode of electrochemical system adhesive, comprise the electrode of this adhesive and comprise the electrochemical system of this electrode |
| CN105914376A (en) * | 2016-06-24 | 2016-08-31 | 辽宁九夷锂能股份有限公司 | Reinforced type composite binder for negative electrode of lithium ion battery and application of reinforced type composite binder |
| CN107359351A (en) * | 2017-06-29 | 2017-11-17 | 郑州大学 | A kind of method that lithium ion battery prepares electrode slice with humic acid base water-based binder and using the binding agent |
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