CN115241457A - Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery - Google Patents
Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 36
- -1 graphene compound Chemical class 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims abstract 2
- 230000000171 quenching effect Effects 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 239000003273 ketjen black Substances 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 239000006229 carbon black Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 8
- 238000004537 pulping Methods 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- H01M4/624—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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 provides a high-performance metal ion battery conductive slurry and a preparation method thereof. The method comprises the steps of obtaining three-dimensional banded graphene through a liquid nitrogen quenching method, mixing the three-dimensional banded graphene and conductive carbon black according to a certain proportion, and performing liquid phase ball milling in a dispersing agent to obtain the high-performance metal ion battery conductive slurry. The conductive paste combines a good space cross-linking network of three-dimensional strip graphene with excellent conductivity of conductive carbon black, and a 'surface-point'/'point-point' contact combination is constructed in an electrode, so that a novel conductive electrode system with a long-range bridging conductive network and a three-dimensional ion migration channel is realized, and a good synergistic effect is realized. The conductive paste has the advantages of simple preparation method, low raw material cost, excellent performance and good application value and prospect.
Description
Technical Field
The invention belongs to the technical field of metal ion battery conductive agents, and particularly relates to high-performance metal ion battery conductive slurry and a preparation method thereof.
Background
A metal ion battery (lithium ion battery, sodium ion battery, potassium ion battery, etc.) is an energy storage device which uses a compound capable of embedding metal ions as positive and negative electrode materials, and the metal ions shuttle back and forth through electrolyte to realize energy storage and release. The metal ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector, a shell and the like, wherein the positive electrode and the negative electrode are the core of the whole battery, and the performance of the metal ion battery directly determines the quality of the energy storage characteristic of the battery. The positive electrode and the negative electrode of the battery mainly comprise active substances, conductive agents, binders and current collectors, wherein the active substances in the electrodes are mainly used for storing metal ions, the conductive agents are used for enhancing the charge transmission capability of the electrodes and promoting the conduction of electrons in the electrodes, and the binders firmly bond the active substances, the conductive agents and the current collectors together to ensure the integrity of the electrodes in the charging and discharging processes.
Although the conductive agent accounts for a small proportion of the components of the metal ion battery, the conductive agent is important for improving the rate performance of the battery and assisting the active material to fully exert the capacity and the cycling stability of the active material. The traditional conductive agents are mainly carbon black and acetylene black. The carbon nano-particles with the microscopic appearance of tens of nanometers to dozens of nanometers are mutually crosslinked to form a coral-shaped structure in space. The traditional conducting agent and active material particles mainly improve the conductivity of the electrode in a point-point contact mode, and the active material and the conducting agent are easy to lose electric contact in the charging and discharging process, so that the electrochemical performance of the electrode is rapidly attenuated. In recent years, new multidimensional conductive agents such as carbon nanotubes (ACS Nano 2021,15, 6735-6746) and graphene conductive agents (Nano Energy 2012,1,429-439, journal of Energy Chemistry 2019,30, 19-26) have attracted increasing attention. Compared with the traditional zero-dimensional conductive agent, the novel multidimensional conductive agent has the remarkable advantages that: 1) The contact mode between the conductive agent and the active material particles is changed from point-point contact to line-point contact and surface-point contact, so that the contact area is increased, and the use efficiency of the conductive agent is improved; 2) The linear and planar conductive agents are beneficial to the construction of a conductive network and improve the transmission efficiency of electrons/ions. However, some key problems also exist when the carbon nanotubes and graphene are directly used as a conductive agent, for example, although the linear structure of the carbon nanotubes enables effective point/line contact to be constructed between the carbon nanotubes and active material particles, the pure physical contact mode of the carbon nanotubes enables insufficient contact between the carbon nanotubes and the active material particles, and the improvement of the cycling stability and rate capability of the carbon nanotubes to electrodes is not obvious; the planar structure characteristics of graphene can inhibit the transmission of metal ions to some extent (especially under a large current), and the rate performance of the electrode material is affected.
The three-dimensional strip-shaped graphene structure (patent grant No. CN 105947973B) self-developed by the applicant is formed by spatially cross-linking graphene nano-strips. The research of the work finds that when the three-dimensional strip graphene is used as a metal ion battery conductive agent, the active material can be tightly wrapped by the unique neural network-shaped multi-antenna structure, so that the 'power loss' of the electrode and the structural crushing of the active material in the charging and discharging process are effectively prevented. Meanwhile, the three-dimensional strip-shaped structure can provide a continuous three-dimensional conductive network, and the transmission efficiency of electrons/ions in the electrode is improved. Compared with graphene, the graphene nanoribbon with the three-dimensional strip-shaped graphene structure has a large length-diameter ratio, and the transmission steric hindrance of metal ions is greatly reduced.
The high-performance metal ion battery conductive slurry (shown in figure 1) is constructed by compounding a three-dimensional strip-shaped graphene structure with traditional conductive carbon black, a space cross-linking network with a good three-dimensional strip-shaped graphene structure is combined with the excellent conductivity of the conductive carbon black, the disadvantages that the traditional conductive agent and an active material are simply dependent on short-distance point-point contact and the utilization rate of the conductive agent is insufficient are changed, surface-point/point-point contact combination is constructed in an electrode, a novel conductive electrode system with a long-distance bridging conductive network and a three-dimensional ion migration channel is provided, and a good synergistic effect is realized, so that the transmission efficiency of electrons/ions in the electrode and the stability of the electrode are improved, and the performances of a plurality of typical conductive agents are shown in table 1.
TABLE 1 comparison of the Properties of different conductive Agents
Disclosure of Invention
The invention aims to construct a high-performance metal ion battery conductive paste. The invention also aims to provide a preparation method of the high-performance metal ion battery conductive slurry.
The high-performance metal ion battery conductive slurry is prepared by mixing three-dimensional strip graphene, conductive carbon black, a liquid dispersion medium and a dispersion auxiliary agent. The mass ratio of solids in the conductive slurry is 30-90%, the mass ratio of three-dimensional strip graphene in the solids is a, the mass ratio of carbon black is b, a + b =100%, and a is more than or equal to 5% and less than or equal to 90%.
Further, the preparation of the three-dimensional strip-shaped graphene is carried out according to the patent already granted by us (patent grant No. CN 105947973B), and the specific preparation parameter conditions are slightly adjusted: preparing a graphene oxide dispersion liquid by adopting an improved Hummers method, wherein a solvent is deionized water, the concentration of the graphene oxide dispersion liquid is 0.3mg/mL, then spraying the graphene oxide dispersion liquid into liquid nitrogen at a speed of 5mL/min, freeze-drying and carrying out heat treatment under the protection of nitrogen to obtain three-dimensional strip graphene, wherein the heat treatment temperature range is 250-1200 ℃, and the heat treatment time is 0.2-10h.
Further, the preparation method of the high-performance metal ion battery conductive slurry comprises the steps of firstly weighing three-dimensional strip graphene and carbon black in a specific proportion, and uniformly dispersing the three-dimensional strip graphene and the carbon black in a solvent, wherein the dispersion method can be one or more of high-speed stirring, ultrasonic treatment, liquid phase grinding and high-speed homogenization, the high-speed stirring dispersion speed is 300-12000 r/min, the ultrasonic treatment frequency is 40kHz, the ultrasonic output power is 60-600W, and the mass ratio of liquid phase grinding ball materials is 5:1, dispersing for 10-2400 minutes, carrying out vacuum filtration on the obtained dispersion liquid to obtain a premix, adding the premix into a proper liquid dispersion medium, adding a certain amount of dispersion auxiliary agent, and carrying out liquid phase ball milling for 10-2400 minutes to obtain the high-performance metal ion battery conductive slurry.
The invention mainly has the following beneficial effects:
the high-performance metal ion battery conductive paste provided by the invention changes the short-range point-point contact mode of the traditional conductive agent, and a novel conductive electrode system which is formed by combining surface-point/point-point contact and has a long-range bridging conductive network and a three-dimensional ion migration channel is constructed in the electrode. Meanwhile, the three-dimensional strip graphene with certain mechanical strength and toughness can effectively prevent the active material from being power-off and structurally crushed in the charging and discharging process, and the cycling stability of an electrode system is improved. The preparation method of the high-performance metal ion battery conductive paste provided by the invention can realize high-performance and long-cycle construction of the metal ion battery, and has good application value and prospect.
Drawings
FIG. 1 is a scanning electron micrograph of a high performance metal ion battery conductive paste;
FIG. 2 is a graph comparing the cycle performance of lithium ion batteries manufactured using the experiment of the present invention and the comparative example;
FIG. 3 is a comparative graph of electrochemical impedance spectra of 300 cycles of charged and discharged lithium ion batteries manufactured by the experiment of the present invention and the comparative example.
Detailed Description
In order to show the objects, technical solutions and advantages of the present invention more clearly, the following description will be made with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
And preparing the Si-based negative pole piece by using the high-performance metal ion battery conductive slurry.
Homogenizing and mixing 10mg of three-dimensional strip graphene and 10mg of carbon black in 20mL of ethanol for 20min by using a high-speed shearing homogenizer, carrying out vacuum filtration and freeze drying to obtain a premix, dispersing the premix in 5mL of deionized water, and carrying out liquid phase ball milling for 1h at the rotating speed of 500 rpm to prepare the high-performance metal ion battery conductive slurry (figure 1). Adding 60mg of nano Si (the distribution range of the particle diameter is 30-100 nm) and 20mg of sodium alginate into the prepared high-performance metal ion battery conductive slurry, preparing electrode slurry through the processes of slurry mixing/pulping/slurry mixing/pulping, and preparing the Si-based negative electrode piece through the processes of coating, baking, rolling and die cutting. And assembling the Si-based negative pole piece, the positive and negative pole shells, the gaskets, the elastic sheets, the lithium sheets, the diaphragms and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Comparative example 1
Carbon black is used as a conductive agent to prepare the Si-based negative pole piece.
60mg of nano Si (the distribution interval of the particle diameters is 30-100 nm), 20mg of carbon black and 20mg of sodium alginate are uniformly mixed, the mixture is subjected to liquid phase ball milling for 1 hour in 5mL of deionized water at the rotating speed of 500 revolutions per minute, electrode slurry is prepared through the processes of slurry mixing/pulping/slurry mixing/pulping, and coating, baking, rolling and die cutting are carried out to prepare the negative electrode plate with the Si-based comparative example. And assembling the comparative Si-based negative electrode plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Example 2
And (3) preparing the lithium iron phosphate-based positive pole piece by using the high-performance metal ion battery conductive slurry.
Homogenizing and mixing 5mg of three-dimensional strip graphene and 5mg of carbon black in 10mL of ethanol for 20min by using a high-speed shearing homogenizer, carrying out vacuum filtration and freeze drying to obtain a premix, dispersing the premix in 5mL of N-methylpyrrolidone (NMP), and carrying out liquid phase ball milling for 1h at the rotating speed of 500 revolutions per minute to prepare the high-performance metal ion battery conductive slurry. Adding 80mg of lithium iron phosphate and 10mg of polyvinylidene fluoride (PVDF) into the prepared high-performance metal ion battery conductive slurry, preparing electrode slurry through the processes of slurry mixing/pulping/size mixing/pulping, and preparing the lithium iron phosphate-based positive electrode piece through the processes of coating, baking, rolling and die cutting. And assembling the lithium iron phosphate-based positive pole piece, the positive and negative pole shells, the gasket, the elastic sheet, the lithium piece, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Comparative example 2
Carbon black is used as a conductive agent to prepare the lithium iron phosphate-based positive pole piece.
Uniformly mixing 80mg of lithium iron phosphate, 10mg of carbon black and 10mg of polyvinylidene fluoride (PVDF), carrying out liquid phase ball milling for 1h in 5mL of N-methylpyrrolidone (NMP) at the rotating speed of 500 revolutions per minute, preparing electrode slurry through the processes of slurry mixing/pulping/slurry mixing/pulping, and carrying out coating, baking, rolling and die cutting to obtain the lithium iron phosphate-based positive electrode piece of the comparative example. And assembling the comparative lithium iron phosphate-based negative electrode plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button half cell in a glove box, and standing for 12h to ensure that the interior of the cell is fully soaked.
The electrochemical performance of the four button half-cells is tested, and the specific test steps and results are as follows:
electrochemical cycle performance tests were performed on the button-type half-cells prepared in the examples and comparative examples, the button-type half-cells were activated for 5 cycles at a current density of 0.5A/g, and then the cycle performance tests were performed at a current density of 1A/g, and the results of comparison of electrochemical cycle performance are shown in FIG. 2. It was found that the capacity retention ratio of comparative example 1 was only 24.3% after 300 cycles of charge and discharge at 1A/g, whereas the capacity retention ratio of example 1 was as high as 69.3%, and the electrode capacity was still as high as 1031.4mAh/g after 300 cycles of charge and discharge. By studying the Electrochemical Impedance (EIS) spectrum of the electrode after 300 cycles of charging and discharging, we find that the electrode of example 1 still maintains lower interface resistance and good electron/ion transmission performance after 300 cycles, and the electrode of comparative example 1 has larger interface resistance and poor electron/ion transmission performance after cycles. The structure that the active Si particles are wrapped by the three-dimensional strip-shaped graphene is considered to avoid direct contact of the Si particles and electrolyte, so that the generation of interface side reactions is reduced, meanwhile, the addition of the three-dimensional strip-shaped graphene is beneficial to forming a thin and stable Solid Electrolyte Interface (SEI) film on the surface of the three-dimensional strip-shaped graphene, and the influence of the thick SEI film formed in the traditional pure carbon black electrode on electron/ion transmission and the continuous consumption of the electrolyte are avoided.
TABLE 2 comparison of specific discharge capacity and cycling performance results
| Item | First circle capacity (mAh/g) | Capacity retention after 300 cycles (%) |
| Example 1 | 2117 | 69 |
| Comparative example 1 | 1824 | 24 |
| Example 2 | 173 | 98％ |
| Comparative example 2 | 169 | 94％ |
In particular, those skilled in the art will recognize that the foregoing examples are illustrative only, and are not limiting. Changes and modifications of the above embodiments are within the scope of the present invention as described above.
Claims (3)
1. A high-performance metal ion battery conductive paste is characterized in that: the graphene material is prepared by mixing three-dimensional banded graphene, conductive carbon black, a liquid dispersion medium and a dispersion auxiliary agent.
2. The high-performance metal-ion battery conductive paste of claim 1, wherein: the mass ratio of the solid is 30-90%, the mass ratio of the three-dimensional strip graphene in the solid is a, the mass ratio of the conductive carbon black is b, a + b =100%, and a is more than or equal to 5% and less than or equal to 90%; the conductive carbon black is one or more of commercially available conductive acetylene black, super P conductive carbon black and Ketjen black; the liquid dispersion medium consists of a solvent and a dispersion auxiliary agent, wherein the solvent can be one or more of deionized water, N-methyl pyrrolidone, N-dimethyl amide and dimethyl sulfoxide for combined use, the dispersion auxiliary agent is one or more of polyvinylpyrrolidone, polyacrylamide, sodium dodecyl sulfate and ethanol for combined use, and the mass percentage of the dispersion auxiliary agent in the liquid dispersion medium is 0-2.0%.
3. A preparation method of high-performance metal ion battery conductive slurry is characterized by comprising the following steps: 1) Obtaining three-dimensional strip-shaped graphene through a liquid nitrogen quenching method and heat treatment, wherein the three-dimensional strip-shaped graphene is formed by spatially crosslinking graphene strips, the length range of the graphene strips is 0.1-200 mu m, the width range of the graphene strips is 0.01-1 mu m, the heat treatment temperature range is 250-1200 ℃, and the heat treatment time is 0.2-10h; 2) Weighing three-dimensional strip graphene and conductive carbon black in a specific ratio; 3) Uniformly dispersing the three-dimensional banded graphene and the conductive carbon black in a solvent, wherein the dispersion method can be one or more of high-speed stirring, ultrasonic treatment and liquid-phase grinding, the high-speed stirring dispersion speed is 300-12000 r/min, the ultrasonic treatment frequency is 40kHz, the ultrasonic output power is 60-600W, and the liquid-phase grinding ball material mass ratio is 5:1, dispersing for 10-2400 minutes; 4) And carrying out vacuum filtration on the obtained dispersion liquid to obtain a premix, adding the premix into a proper liquid dispersion medium, adding a certain amount of dispersing auxiliary agent, and carrying out liquid phase ball milling for 10-2400 minutes to obtain the high-performance metal ion battery conductive slurry.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210715221.1A CN115241457B (en) | 2022-06-22 | 2022-06-22 | Three-dimensional ribbon graphene compound conductive slurry for metal ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210715221.1A CN115241457B (en) | 2022-06-22 | 2022-06-22 | Three-dimensional ribbon graphene compound conductive slurry for metal ion battery |
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| CN115241457A true CN115241457A (en) | 2022-10-25 |
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| CN105932287A (en) * | 2016-05-24 | 2016-09-07 | 宁波墨西科技有限公司 | Graphene composite conductive agent and preparation method thereof |
| CN105947973A (en) * | 2016-06-16 | 2016-09-21 | 哈尔滨工程大学 | Tentacle-type graphene nanostructure unit, graphene-based composite material with topological structure and preparation method |
| CN106784827A (en) * | 2016-12-19 | 2017-05-31 | 中国科学院电工研究所 | Mesoporous graphene conductive slurry and Preparation method and use |
| CN109903931A (en) * | 2019-02-25 | 2019-06-18 | 天津艾克凯胜石墨烯科技有限公司 | A kind of preparation method of high dispersive graphene composite conductive slurry |
| CN110391418A (en) * | 2018-04-18 | 2019-10-29 | 常州墨之萃科技有限公司 | A kind of High-performance graphene composite conducting slurry and preparation method thereof |
| CN112331380A (en) * | 2020-11-03 | 2021-02-05 | 松山湖材料实验室 | Composite conductive slurry and preparation method and application thereof |
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Patent Citations (6)
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| CN105932287A (en) * | 2016-05-24 | 2016-09-07 | 宁波墨西科技有限公司 | Graphene composite conductive agent and preparation method thereof |
| CN105947973A (en) * | 2016-06-16 | 2016-09-21 | 哈尔滨工程大学 | Tentacle-type graphene nanostructure unit, graphene-based composite material with topological structure and preparation method |
| CN106784827A (en) * | 2016-12-19 | 2017-05-31 | 中国科学院电工研究所 | Mesoporous graphene conductive slurry and Preparation method and use |
| CN110391418A (en) * | 2018-04-18 | 2019-10-29 | 常州墨之萃科技有限公司 | A kind of High-performance graphene composite conducting slurry and preparation method thereof |
| CN109903931A (en) * | 2019-02-25 | 2019-06-18 | 天津艾克凯胜石墨烯科技有限公司 | A kind of preparation method of high dispersive graphene composite conductive slurry |
| CN112331380A (en) * | 2020-11-03 | 2021-02-05 | 松山湖材料实验室 | Composite conductive slurry and preparation method and application thereof |
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