CN113540462A - Ferric oxide-based negative electrode binder of lithium ion battery - Google Patents
Ferric oxide-based negative electrode binder of lithium ion battery Download PDFInfo
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Abstract
The invention discloses a lithium ion battery ferroferric oxide-based negative electrode binder, wherein PAM with low cost, high viscosity and high mechanical strength is selected as the binder, and PAM aqueous solution with high viscosity and high mechanical strength is obtained through simple dissolution and stirring. Compared with the traditional PVDF binder, the PAM effectively binds the electrode active material by virtue of high viscosity, and keeps good electrical contact of the electrode material. In addition, the excellent mechanical strength of PAM makes it well able to withstand Fe3O4The problems of huge volume change, electrode disintegration, crushing and the like caused by chemical changes such as lithium intercalation and lithium removal in the cycle process of the cathode and the anode, the structural integrity of the electrode is kept, and the cycle stability of the electrode is further realized. The PAM binder also enables stable cycling conditions under negative high loading conditions. PAM Binder for high-load Fe3O4The stable cycling of the cathode shows that the binder is further pushed in the lithium ion batteryHas wide application prospect.
Description
Technical Field
The invention belongs to the technical field of binder application and electrochemistry, and relates to a ferric oxide-based negative binder of a lithium ion battery, wherein the binder is green, low in cost, high in viscosity and high in mechanical strength and is water-soluble polyacrylamide.
Background
The development of low cost, high safety and high energy density large scale energy storage systems to accommodate the rapidly growing demand for renewable energy has attracted considerable interest. Lithium ion batteries have the advantages of high energy density, long cycle life, and the like, are considered to be the most promising energy storage devices, and have been widely used in portable electronic devices, such as smart phones, smart wearable devices, and computers. However, to promote its large-scale application in electric vehicles and smart grids, it is necessary to meet the requirements of excellent energy density, ultra-long service life and inexpensive economic cost. High capacity electrode materials are critical for high energy density lithium ion batteries. Fe3O4Due to its high theoretical capacity (926mAh g)-1) But are considered promising anode materials. Fe in the circulation process3O4The volume change of (a) seriously damages the integrity of the electrode, resulting in Fe3O4The electrochemical performance of the base cathode is poor. In order to solve the problem, researchers design a carbon coating as a buffer layer or a conductive substrate, so that the crushing of an electrode is reduced, and the conductivity is improved, thereby improving the cycling stability of the battery. Another strategy is to design nanostructured Fe3O4Base material containing Fe in cyclic process by its void structure3O4To maintain the integrity of the electrode. However, the above strategy violates the principle of area capacity oriented in high energy density lithium ion batteries.
The binder is used as an important component of the electrode, and can remarkably enhance the electrochemical performance of the electrode, especially for a high-capacity active material with large volume change. However, to date, binders have been targeted to increase Fe3O4Base powerThe work on the electrochemical performance of the electrodes is rarely reported. The traditional polyvinylidene fluoride (PVDF) binder consumes a large amount of expensive and toxic organic solvent N-methyl pyrrolidone (NMP) in the using process, and is not in accordance with the development concept of green chemical industry. Development of a water-based binder having high viscosity to replace the conventional PVDF is receiving increasing attention.
Disclosure of Invention
The invention aims at Fe3O4The integrity of the electrode is seriously damaged due to the huge volume change generated by lithium intercalation and lithium removal in the cycle process of the cathode, so that the problem of poor battery cycle stability is caused, and Polyacrylamide (PAM) is developed as Fe3O4The water system binder based on the negative electrode replaces the traditional PVDF binder.
The invention is realized by adopting the following technical scheme:
the lithium ion battery ferroferric oxide-based negative electrode binder is water-soluble PAM with high viscosity and high mechanical strength.
In the above technical solution, further, the preparation process of the triiron tetroxide-based negative electrode binder for the lithium ion battery, which is used as the triiron tetroxide-based negative electrode binder, specifically includes the following steps:
(1) respectively preparing CH with a certain concentration3COONa and FeCl3·6H2And O, ethylene glycol solution is added, and ultrasonic mixing is carried out to be uniform.
(2) The homogeneous solution obtained in step (1) was transferred to a Teflon-lined stainless steel autoclave and heated at 150 ℃ and 250 ℃ for 24 h.
(3) Collecting the precipitated Fe after the reaction in the step (2) by using a magnet3O4The nanospheres are washed sequentially with deionized water and ethanol.
(4) Taking the Fe in the step (3)3O4Nanospheres in 0.1mol L-1HNO3Ultrasonically dispersing in the solution, washing with deionized water for three times, and dispersing the obtained product into glucose solution with a certain concentration.
(5) Transferring the uniform solution obtained in the step (4) into an autoclave, and heating at 140 ℃ and 180 ℃ for 16 h.
(6) And (5) collecting the precipitate in the step (5), washing with deionized water and ethanol in sequence, and drying.
(7) Charging the sample obtained in step (6) into a tube furnace at N2Heating for 4 hours at 350-450 ℃ in the atmosphere.
(8) Putting the sample obtained in the step (7) into HCl solution with certain concentration to obtain porous Fe3O4@ C nanospheres.
(9) And (2) selecting a chemically pure water-soluble polymer PAM to disperse and dissolve in deionized water to obtain a PAM aqueous solution with a certain concentration, and using the PAM aqueous solution as the iron-based negative electrode binder prepared in the step.
Further, the concentration of the PAM solution in the step (9) is 1-2 wt%;
further, the concentration of HCl etching selected in the step (8) is 3mol L-1The etching time is 3 h.
The PAM binder with high viscosity and high mechanical property is used as Fe of the lithium ion battery3O4And (3) application of the cathode binder.
In the present invention, since PAM has high adhesion and excellent mechanical properties, Fe can be efficiently contained3O4And maintaining the structural stability of the electrode. In addition, the water-soluble PAM binder enables the preparation of Fe in a green, low cost process compared to PVDF3O4The cathode is based, thereby avoiding the use of expensive and toxic NMP. Fe using PAM binder3O4Base electrode (Fe)3O4@ C-PAM) exhibits a higher rate of performance than electrodes (Fe) using PVDF binder3O4@ C-PVDF). In particular, when Fe3O4@ C loading of 1.8mg cm-2Of (i) Fe3O4@ C-PAM exhibits stable cycle performance; when Fe3O4@ C loading increased to 6.8mg cm-2Of (i) Fe3O4The @ C-PAM negative electrode reaches 8.06mAh cm-2High surface area capacity.
The invention has the following beneficial effects:
(1) the invention provides a P with high viscosity and high mechanical propertyAM binder for lithium ion battery Fe3O4Based on the negative electrode, effectively solves the problem that Fe is caused by insufficient binding capacity and poor mechanical property when PVDF is used as a binder3O4The base electrode structure is crushed and the cycle performance is poor. Compared with Fe3O4@C-PVDF，Fe3O4The @ C-PAM negative electrode shows higher elastic modulus and hardness, and illustrates that the PAM has better mechanical strength and can more effectively contain the Fe in circulation3O4The volume of the base anode changes. Atomic Force Microscope (AFM) viscosity force tests prove that the adhesion force of PAM is far higher than that of PVDF, and the PAM plays an important role in maintaining good electrical contact of electrode active materials.
(2) The surface capacity of the electrode determines the total capacity of the electrode and thus the energy density of the battery as a whole. Developing an electrode with high mass loading is a very effective way to increase its surface capacity. Fe prepared based on PAM with high viscosity and high mechanical property3O4Basic negative electrode, when Fe3O4@ C mass loading of 1.8mg cm-2At 0.1C rate, after 61 cycles, the solution keeps 1.15mAh cm-2Discharge specific capacity and capacity retention rate as high as 82.3%. The loading was 4.6mg cm-2Then, the sample remained 1.81mAh cm after 50 cycles under the same test conditions-2Specific discharge capacity of (2). When Fe3O4@ C loading was further increased to 6.8mg cm-2The first circle shows up to 8.06mAh cm-2Specific discharge capacity and a high first-turn coulombic efficiency (ICE) of 67.2%. Similar ICE was demonstrated regardless of high or low loading electrode, demonstrating that the interfacial stability of the different loading electrodes is comparable during the initial activation phase, further illustrating the use of PAM as high area capacity Fe3O4The high efficiency of the @ C-based negative electrode binder.
(3) The PAM binder provided by the invention avoids the problems of pollution and the like caused by a toxic and harmful organic reagent NMP (N-methyl pyrrolidone) in the application of the traditional PVDF binder.
Drawings
FIG. 1 is an AFM viscous force test of PAM and PVDF binders.
FIG. 2 is Fe3O4@ C-PVDF and Fe3O4Nano indentation test pattern of @ C-PAM electrode: (a) modulus of elasticity; (b) hardness;
FIG. 3 is Fe3O4@ C-PAM and Fe3O4A plot of the cycling performance of the @ C-PVDF electrode at 0.2C;
FIG. 4 is Fe3O4The circulating performance of the @ C-PAM electrode at 0.1C multiplying power is 1.8mg cm-2；
FIG. 5 is Fe3O4The circulating performance of the @ C-PAM electrode at 0.1C multiplying power is 4.6mg cm-2；
FIG. 6 is Fe3O4The circulating performance of the @ C-PAM electrode at 0.1C multiplying power is 6.8mg cm-2；
FIGS. 7(a) and (b) are each Fe3O4@ C-PVDF and Fe3O4The negative electrode of @ C-PAM is 0.5A g-1SEM images at different magnifications after 50 cycles of lower cycle; (c) and (d) is Fe3O4@ C-PVDF and Fe3O4The negative electrode of @ C-PAM is 0.5A g-1SEM images after 50 cycles of the lower cycle; (e) and (f) is Fe3O4The negative electrode of @ C-PAM is 0.5A g-1High resolution SEM images after 50 cycles of lower cycle.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A water-soluble PAM with high viscosity and high mechanical strength is used as a triiron tetroxide-based negative electrode binder, and the following preparation process of related materials comprises the following steps:
(1) respectively preparing CH with a certain concentration3COONa and FeCl3·6H2And O, ethylene glycol solution is added, and ultrasonic mixing is carried out to be uniform.
(2) The homogeneous solution obtained in step (1) was transferred to a Teflon-lined stainless steel autoclave and heated at 150 ℃ and 250 ℃ for 24 h.
(3) Collecting the reaction in the step (2) by using a magnetPost-precipitation of Fe3O4And washing with deionized water and ethanol sequentially.
(4) Taking the Fe in the step (3)3O4Nanospheres in 0.1mol L-1HNO3Ultrasonically dispersing in the solution, washing with deionized water for three times, and dispersing the obtained product into glucose solution with a certain concentration.
(5) Transferring the uniform solution obtained in the step (4) into an autoclave, and heating at 140 ℃ and 180 ℃ for 16 h.
(6) And (5) collecting the precipitate in the step (5), washing with deionized water and ethanol in sequence, and drying.
(7) Charging the sample obtained in step (6) into a tube furnace at N2Heating for 4 hours at 350-450 ℃ in the atmosphere.
(8) Putting the sample obtained in the step (7) into HCl solution with certain concentration to obtain porous Fe3O4@ C nanospheres.
(9) And (2) selecting a chemically pure water-soluble polymer PAM, dispersing and dissolving the PAM in deionized water to obtain a PAM aqueous solution with a certain concentration, and using the PAM aqueous solution as the iron-based negative electrode binder prepared in the step.
According to the scheme, the concentration of the PAM solution in the step (9) is 1-2 wt%;
according to the scheme, the concentration of HCl etching selection in the step (8) is 3mol L-1The etching time is 3 h.
The adhesion of the PAM and PVDF binders was characterized by AFM adhesion testing. Fig. 1 shows that the binding force of PAM is 30.91nN, which is much higher than 2.97nN of PVDF, and quantitatively demonstrates the high viscosity characteristic of PAM as a negative binder, which is beneficial to maintaining good electrical contact between the electrode active material and other components. Characterization of Fe by nanoindentation testing3O4@ C-PAM and Fe3O4Mechanical Strength of the @ C-PVDF electrode, FIG. 2 shows Fe3O4The elastic modulus and hardness of the @ C-PAM are both higher than that of Fe3O4@ C-PVDF, proving that PAM binder has sufficient mechanical strength to effectively withstand Fe3O4The problems of huge volume change, electrode crushing and cracking and the like caused by lithium intercalation and lithium removal in the charging and discharging processes of the base cathodeThe structural integrity of the electrode and the stability of the cycle performance are maintained. The invention discloses a PAM polymer with high viscosity and high mechanical property as Fe of a lithium ion battery3O4And (3) a negative electrode binder. The other steps of the preparation method of the cathode are consistent with the conventional preparation method, and Fe is adopted3O4@ C is an active material, Super P is a conductive agent, PAM is a binder, and the mass ratio of the active material to the conductive agent to the binder is 7:2: 1; mixing them in deionized water according to a certain proportion to form uniform slurry, then coating the slurry on the copper current collector. The coated pole piece was placed in an oven at 80 ℃ for 12 hours. Preparation of PVDF Fe as binder with NMP as solvent by the same method3O4And a cathode. LiPF at 1M6The lithium ion battery is dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC) to be used as electrolyte, a lithium sheet is used as a negative electrode, Celgard 2325 is used as a diaphragm, and CR 2025 type stainless steel is used as a battery shell to assemble the button lithium ion battery.
Fe after 120 cycles of 0.2C cycle, as shown in FIG. 33O4@ C-PAM exhibits a significantly higher value than Fe3O4Discharge capacity of @ C-PVDF electrode, confirming Fe3O4@ C-PAM has a ratio of Fe to3O4@ C-PVDF has better cycle performance. FIG. 4 shows, under the conditions of the rate test, when Fe3O4The mass loading of @ C-PAM is 1.8mg cm-2Then, after the circulation of 0.1C for 61 circles, the 1.15mAh cm is still kept-2Discharge surface capacity and first efficiency of 82.3%. When the loading amount is 4.6mg cm-2When (FIG. 5), Fe3O4The @ C-PAM can keep 1.81mAh cm after circulating for 50 circles-2The discharge surface capacity of (1). When the loading capacity is further increased to 6.8mg cm-2In time (FIG. 6), the electrode showed a first turn of 8.06mAh cm-2The capacity of the discharge surface is high, and the first efficiency is as high as 67.2 percent and can be 3mAh cm-2The lower cycle of the face volume of (1) is nearly 30 cycles. FIG. 7 is Fe3O4@ C-PAM and Fe3O4SEM images before and after @ C-PVDF pole piece cycle. Before the circulation, the surface topography of the two is basically consistent, however, after 50 cycles of the circulation, Fe3O4The surface of the @ C-PVDF pole piece has obvious cracks, while Fe3O4The surface of the @ C-PAM is still relatively flat, no obvious crack exists, the PAM can be better bonded with each component in the circulating process, and meanwhile, the composite material has good mechanical property, can effectively contain the volume expansion of a silicon negative electrode in the circulating process, and reduces the electrode crushing and powdering. Therefore, the PAM binder which is green and pollution-free and has high viscosity and high mechanical property has great potential in future application.
Claims (4)
1. The lithium ion battery ferroferric oxide-based negative electrode binder is characterized in that the binder is water-soluble PAM with high viscosity and high mechanical strength.
2. The lithium ion battery iron tetroxide-based negative electrode binder as claimed in claim 1, wherein the preparation process for the iron tetroxide-based negative electrode binder specifically comprises the following steps:
(1) separately prepare CH3COONa and FeCl3·6H2Glycol solution of O, and ultrasonic mixing;
(2) transferring the uniform solution obtained in the step (1) into a Teflon stainless steel autoclave with a lining, and heating for 24h at the temperature of 150-;
(3) collecting the precipitated Fe obtained after the reaction in the step (2) by using a magnet3O4The nanospheres are washed by deionized water and ethanol in sequence;
(4) taking the Fe in the step (3)3O4Nanospheres in 0.1mol L-1 HNO3Ultrasonically dispersing in the solution, washing with deionized water, and dispersing the obtained product into glucose solution;
(5) transferring the uniform solution obtained in the step (4) into an autoclave, and heating for 16h at 140-;
(6) collecting the precipitate in the step (5), washing with deionized water and ethanol in sequence, and drying;
(7) charging the sample obtained in step (6) into a tube furnace at N2Heating for 4 hours at 350-450 ℃ in the atmosphere;
(8) placing the sample obtained in the step (7) in HCl solutionEtching to obtain porous Fe3O4@ C nanospheres;
(9) and (3) dispersing and dissolving chemically pure water-soluble polymer PAM in deionized water to obtain a PAM aqueous solution, and using the PAM aqueous solution as the iron-based negative electrode binder prepared in the steps (1) to (8).
3. The lithium ion battery triiron oxide-based negative electrode binder of claim 2, wherein: and (4) the concentration of PAM in the PAM aqueous solution in the step (9) is 1-2 wt%.
4. The lithium ion battery triiron oxide-based negative electrode binder of claim 2, wherein: the concentration of the HCl etching in the step (8) is 3mol L-1The etching time is 3 h.
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| CN101794884A (en) * | 2010-04-01 | 2010-08-04 | 安徽工业大学 | Part of hydrolyzed polyacrylamide bonding agent used for forming negative electrode of lithium ion battery |
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| CN103219511A (en) * | 2013-03-28 | 2013-07-24 | 浙江大学 | Ferroferric oxide/carbon composite material with tubular core-shell structure as well as preparation method and application thereof |
| CN104167536A (en) * | 2014-07-09 | 2014-11-26 | 浙江大学 | Preparation method and purpose thereof of spherical ferriferrous oxide nano particles with controllable size |
| CN109095510A (en) * | 2018-09-14 | 2018-12-28 | 江苏省家禽科学研究所 | Ferroferric oxide nano granules and preparation method thereof and the application in inhibition salmonella proliferation |
| CN109133189A (en) * | 2018-09-17 | 2019-01-04 | 河北工业大学 | The preparation method of carbon coated ferriferrous oxide nanoshell supported nano-gold particle |
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- 2021-07-02 CN CN202110748686.2A patent/CN113540462A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101794884A (en) * | 2010-04-01 | 2010-08-04 | 安徽工业大学 | Part of hydrolyzed polyacrylamide bonding agent used for forming negative electrode of lithium ion battery |
| CN103219511A (en) * | 2013-03-28 | 2013-07-24 | 浙江大学 | Ferroferric oxide/carbon composite material with tubular core-shell structure as well as preparation method and application thereof |
| CN103208625A (en) * | 2013-04-24 | 2013-07-17 | 北京科技大学 | Preparation method of ferroferric-oxide-based high-performance negative electrode material for lithium ion battery |
| CN104167536A (en) * | 2014-07-09 | 2014-11-26 | 浙江大学 | Preparation method and purpose thereof of spherical ferriferrous oxide nano particles with controllable size |
| CN109095510A (en) * | 2018-09-14 | 2018-12-28 | 江苏省家禽科学研究所 | Ferroferric oxide nano granules and preparation method thereof and the application in inhibition salmonella proliferation |
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