CN114843451A - Preparation method of nontoxic and economical positive pole piece of sodium-ion battery - Google Patents
Preparation method of nontoxic and economical positive pole piece of sodium-ion battery Download PDFInfo
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- CN114843451A CN114843451A CN202210531099.2A CN202210531099A CN114843451A CN 114843451 A CN114843451 A CN 114843451A CN 202210531099 A CN202210531099 A CN 202210531099A CN 114843451 A CN114843451 A CN 114843451A
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- ion battery
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 231100000252 nontoxic Toxicity 0.000 title abstract description 7
- 230000003000 nontoxic effect Effects 0.000 title abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 64
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- 239000013543 active substance Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 30
- 239000002041 carbon nanotube Substances 0.000 claims description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 26
- 239000007772 electrode material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 18
- 238000001652 electrophoretic deposition Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 40
- 238000012360 testing method Methods 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910000398 iron phosphate Inorganic materials 0.000 description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000012876 topography Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000000457 tarsus Anatomy 0.000 description 1
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Images
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a non-toxic and economical positive pole piece of a sodium-ion battery, belonging to the field of positive pole materials of sodium-ion batteries. The preparation method comprises the following steps: firstly mixing an electrode active substance, a conductive agent and a dispersing agent in deionized water to prepare a dispersion liquid, then immersing a counter electrode and a current collector in the dispersion liquid and applying a certain voltage to deposit the mixed substance formed by the active substance, the conductive agent and the dispersing agent on the current collector, and finally drying and rolling the deposited current collector to obtain the positive pole piece. The preparation method has no participation of organic solvent, can effectively control the thickness of the deposition layer by changing the electrophoretic deposition voltage or deposition time, realizes the high-efficiency utilization of the raw materials, provides a way with simple and convenient operation, controllable active loading capacity, environmental protection, no toxicity and high economic benefit for preparing the positive pole piece of the sodium-ion battery, and is beneficial to the development of the positive pole piece of the sodium-ion battery.
Description
Technical Field
The invention relates to the field of positive electrode materials of sodium-ion batteries, in particular to a preparation method of a non-toxic and economical positive electrode plate of a sodium-ion battery.
Background
In the research of secondary energy storage batteries, lithium ion batteries have made a great breakthrough first, and have successfully achieved commercialization in the last 90 th century, and are widely used in mobile phones and portable computers. In recent years, automobiles using lithium ion batteries as power parts gradually replace traditional fuel oil automobiles due to the fact that the automobiles conform to the green development concept, the application field of the lithium ion batteries is further improved, meanwhile, the consumption of lithium resources is also aggravated, and the cost of the lithium ion batteries is increasingly increased. By 2015, the worldwide lithium resource storage capacity is 3978 ten thousand tons and the exploitable lithium resource storage capacity is 1350 ten thousand tons, and with the gradual increase of the demand for lithium, the lithium resource is bound to be in shortage in the future. Therefore, in order to find new energy materials that can replace lithium ion batteries and battery technologies that are cheaper and more efficient than lithium ions, research on sodium ion batteries has been started since the last 80 th century. The working principle of the sodium ion battery is similar to that of lithium ion, and although the theoretical energy density of sodium is lower than that of lithium, sodium has a standard potential higher than that of lithium, which is beneficial to improving the safety of the battery, and the content of sodium resources is high in both crusta and seawater, so that the extraction process is easier compared with the lithium resources. Therefore, from the perspective of resource content and cost, the sodium ion battery has a great application prospect in the field of large-scale energy storage, and has an important significance in the research of the sodium ion battery.
The traditional preparation method of the electrode plate of the sodium-ion battery is characterized in that an electrode active substance, a conductive agent, a binder and a solvent are mixed according to a certain proportion to form slurry, then the slurry is adhered to a current collector in a spraying or pouring mode, the coated current collector is dried, and then a proper part is cut to obtain the electrode plate required by the assembled battery, the performance of the prepared electrode plate is influenced by factors such as slurry viscosity, moving speed of a film coater and the like, the utilization rate of raw materials is low, the thickness of a coating layer of the electrode plate is not easy to regulate, the coating method uses the most extensive binder of polyvinylidene fluoride (PVDF) and needs to be dissolved by an organic reagent of N-methyl pyrrolidone (NMP), the organic reagent has strong toxicity and great harm to the health of a human body, meanwhile, the NMP with a higher boiling point makes the NMP easy to remain in the electrode plate and difficult to remove, and has great influence on the performance of the electrode plate, therefore, there is a need to find a simple, controllable active loading, and green and economical method for preparing an electrode with excellent performance.
In recent years, the electrophoretic deposition method has attracted attention in sodium ion batteries, and the electrophoretic deposition method (EPD) is a preparation process capable of constructing inorganic substances, polymers or compounds with different properties into a coating or a thin film material, and the method is easy to control in operation, simple in equipment and capable of forming a film with uniform thickness on a substrate with a complex shape, and at present, electrophoretic deposition has been widely applied in the research fields of photoelectricity, photocatalysis, biomedicine, energy and the like, and is also applied to the preparation of a sodium ion battery cathode plate, but has not been applied to the preparation of a sodium ion battery cathode material electrode, and a liquid phase solution used in other applications is an organic reagent, has a poor application range, and cannot be generally applied to the preparation of the sodium ion battery cathode plate, so if a green and nontoxic electrophoretic deposition dispersion liquid system with wide applicability is designed, the application of the electrophoretic deposition method in the sodium-ion battery anode system can be widened.
Disclosure of Invention
The invention designs a green and nontoxic dispersion system, and prepares a positive pole piece of a sodium-ion battery by an electrophoretic deposition method, so as to solve the problems that an organic reagent has strong toxicity, influences the performance of the pole piece and is uncontrollable in the electrode active substance loading capacity in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a positive pole piece of a sodium-ion battery comprises the following steps:
and 3, compacting the current collector dried in the step 2, and cutting the current collector into a circular positive pole piece.
Preferably, the electrode active material is a polyanionic compound, and the electrode active material includes FePO 4 、NaFePO 4 、Na 2 FeP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )、Na 3 V 2 (PO 4 ) 3 、Na 2 FePO 4 F。
Preferably, the particle size of the electrode active material ranges from 30nm to 300 nm.
Preferably, the conductive agent is a carbon-based material, and the conductive agent comprises carbon nanotubes, graphene and conductive carbon black.
Preferably, the dispersant comprises cetyltrimethylammonium bromide (CTAB), poly [1- [4- (3-carboxy-4-hydroxyphenylazo) benzenesulfonylamino ] ethanediyl, sodium salt ] (PAZO), or Benzoic Acid (BA).
Further, the mass ratio of the electrode active material, the conductive agent and the dispersing agent is 200: (100-200): (20-200).
Further, the counter electrode is a platinum electrode, and the current collector comprises an aluminum foil, a stainless steel sheet, a zinc sheet and a copper sheet.
Further, the counter electrode and the current collector are parallel to each other in the dispersion liquid, and the distance between the counter electrode and the current collector is 18-22 mm.
Further, the deposition voltage in step 2 is 15V, and the deposition time is 15 min.
And further, the temperature of the vacuum oven is 60-100 ℃, and the vacuum degree is less than 100 pa.
The invention has the following beneficial effects:
polyanion compounds are used as electrode active substances, the electrode active substances, conductive agents and dispersing agents are mixed in water according to a certain proportion to prepare dispersion liquid, then counter electrodes and a current collector are immersed in the dispersion liquid and voltage is applied to the counter electrodes and the current collector, so that mixed substances formed by the active substances, the conductive agents and the dispersing agents are deposited on the current collector, and finally the deposited current collector is compacted to obtain the positive pole piece. The preparation method has no organic solvent, reduces the harm to human body, adds dispersant, increases the dispersibility of active particles and the adhesiveness between the active particles and a current collector, and adds conductive agent for enhancing the electronic conductivity of the electrode. In addition, the loading capacity of the electrode active substance can be adjusted by changing the electrophoretic deposition parameters, so that the raw materials are efficiently utilized, and an approach with simple operation, environmental friendliness, no toxicity and high economic benefit is provided for preparing the positive pole piece of the sodium-ion battery.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of an electrophoretic deposition process using a cathode deposition method;
FIG. 2 is a graph of electrophoretic deposition kinetics for different deposition parameters and dispersion systems in examples 2 and 3, in which: (a) is only FePO 4 The dispersion liquid of (a) is a graph containing FePO alone at different deposition voltages 4 The dispersion liquid system of (c) is a FePO-containing dispersion liquid system under different deposition time 4 CNTs and CTAB in different deposition voltages, (d) is FePO containing 4 Graphs of the dispersion liquid systems of CNTs and CTAB at different deposition times;
FIG. 3 is a real-time image of the positive electrode plate prepared under the conditions of deposition voltage of 15V and deposition time of 10min for different dispersion liquid systems in example 2, wherein: (a) is only FePO 4 The (b) is FePO-containing dispersion liquid system 4 A dispersion system of CNTs and CTAB;
FIG. 4 is FePO of example 4 4 And the surface SEM topography of the positive pole piece prepared by the dispersion with the ratio of CNTs to CTAB of 1: 1 under different deposition voltages and the deposition time of 15min, wherein: (a) a positive pole piece prepared at a deposition voltage of 10V, and (b) a deposition voltageA positive pole piece prepared at 15V, and (c) a positive pole piece prepared at a deposition voltage of 20V;
fig. 5 is surface SEM topography (a-c) and thermogravimetric plots (d-f) of the positive electrode sheets prepared in experiment group one, experiment group two, and experiment group three of example 5, in which: (a) and (d) a surface SEM topography and a thermogravimetric plot of the first experimental group, (b) and (e) a surface SEM topography and a thermogravimetric plot of the second experimental group, and (c) and (f) a surface SEM topography and a thermogravimetric plot of the third experimental group;
fig. 6 is SEM topography of the surface of the positive electrode sheet of the control group and the experimental group three in example 5, in which: (a) is only FePO 4 The positive pole piece prepared by the dispersion liquid system of (b) is FePO containing 4 The positive pole piece is prepared by a dispersion liquid system of CNTs and CTAB;
fig. 7 is a graph of rate performance of sodium ion half cells prepared in experiment group one, experiment group two, and experiment group three of example 5;
fig. 8 is a graph of the cycle performance of the sodium ion half cells prepared in experiment group two and experiment group three in example 5;
fig. 9 is a first three-cycle charge-discharge curve of the sodium ion half-cell prepared in the control group and the experimental group three in example 5, in which: (a) is only FePO 4 The sodium ion half cell prepared by the dispersion liquid system of (b) is FePO containing 4 The sodium ion half-cell prepared by the dispersion system of the CNTs and the CTAB has 1 circle of charge-discharge curve, 2 circle of charge-discharge curve and 3 circle of charge-discharge curve.
The reference numbers are as follows: 1. an electrode holder; 2. a counter electrode; 3. a current collector; 4. electrophoretic deposition of the dispersion; 5. a power supply for the electrophoresis apparatus; 6. an electrophoretic deposition pool.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. The experimental procedures in the following examples are, unless otherwise specified, all of which are conventional.
Example 1: preparation method of non-toxic and economical positive pole piece of sodium-ion half-cell
According to the deposition process shown in fig. 1, the preparation method of the positive electrode plate of the sodium-ion half-cell comprises the following steps:
(1) the iron phosphate (FePO) with the particle diameter of between 100 and 300nm as an electrode active material 4 ) Mixing conductive agent Carbon Nano Tubes (CNTs) and dispersant Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water according to a certain proportion (wherein FePO 4 Concentration of 1g/L), stirring for 5min, and then performing ultrasonic treatment for 10min to obtain uniform dispersion liquid 4, and then pouring the obtained dispersion liquid 4 into an electrophoretic deposition tank 6;
(2) fixing a counter electrode 2(30 x 55mm platinum sheet) and a current collector 3(30 x 55mm aluminum foil) with the thickness of 0.5mm in an electrophoretic deposition pool 6 by using an electrode clamp 1 at room temperature, so that the counter electrode 2 and the current collector 3 are immersed in the dispersion liquid 4 prepared in the step (1), adjusting the distance between the counter electrode 2 and the current collector 3 to be 20mm, turning on an electrophoresis apparatus power supply 5(DYY-7C, six Biotech limited company, Beijing), applying a certain deposition voltage between the counter electrode 2 and the current collector 3, depositing a mixed substance formed by an electrode active substance, a conductive agent and a dispersing agent on the current collector 3 after continuously depositing for a period of time, placing the deposited current collector 3 into a vacuum oven at 70 ℃, vacuumizing so that the vacuum degree of the vacuum oven is less than 100pa, and drying for 12 hours.
(3) And (3) compacting the dried current collector 3 in the step (2) on a roller press (MR-100A, Shenzhenjian crystal), and then stamping into a circular pole piece with the diameter of 12mm to obtain the positive pole piece of the sodium-ion half-cell.
Example 2: analyzing the influence of different deposition voltages on the loading of electrode active materials
1. Preparation of Positive electrode sheet
The preparation method is the same as example 1, except that:
a. setting a control group and an experimental group, wherein the experimental group is prepared by adding iron phosphate (FePO) as an electrode active material 4 ) The conductive agent Carbon Nano Tubes (CNTs) and the dispersant (CTAB) are deionized according to the mass ratio of 1: 1Mixing in water; the control group is FePO 4 Dissolving the mixture in deionized water at the concentration of 1 g/L;
b. deposition voltages of 5V, 10V, 15V, 20V, 25V, 30V, 35V, 40V were applied between the counter electrode 2 and the current collector 3 of the control group or experimental group, respectively, for deposition for 10 min.
2. Calculating the loading of the electrode active material
The loading of the electrode active material was obtained by weighing the mass change before and after the deposition of the current collector 3 with an electronic balance (BSA124S-CW, sartorius, germany).
As can be seen from fig. 2(a) and 2(c), the loading amount of iron phosphate increases and then decreases as the deposition voltage increases in both the control group and the experimental group, and the control group and the experimental group have higher deposition rates at the deposition voltage of 10V to 20V.
Fig. 3(a), (b) are real images of the positive electrode plate prepared under the conditions of 15V deposition voltage and 10min deposition time for the control group and the experimental group, respectively. As can be seen from FIG. 3(a), the dispersion system is only FePO 4 The binding force between the pole piece prepared by electrophoretic deposition and the current collector is poor, and FePO is used in the process of stamping the pole piece 4 The falling is easy to occur; from 3(b), it is known that addition of CTAB can result in FePO 4 CNTs are uniformly deposited and attached to a current collector, and the deposition layer does not fall off under certain deformation.
In conclusion, the deposition voltage of 15V is selected to be used for subsequent experiments by combining the manufacturing cost and the loading capacity of the iron phosphate.
Example 3: analyzing the influence of different deposition times on the loading of the electrode active material
1. Preparation of Positive electrode sheet
The preparation method is the same as example 1, except that:
a. setting a control group and an experimental group, wherein the experimental group is prepared by adding iron phosphate (FePO) as an electrode active material 4 ) Mixing a conductive agent Carbon Nano Tube (CNTs) and a dispersant (CTAB) in deionized water according to the mass ratio of 1: 1; the control group is FePO 4 Dissolving the mixture in deionized water at the concentration of 1 g/L;
b. a deposition voltage of 15V is applied between the counter electrode 2 and the current collector 3 of the control group or the experimental group, and deposition is continued for 5min, 10min, 13min, 15min, 18min, 20min and 25min respectively.
2. Calculating the loading of the electrode active material
The weighing method was the same as in example 2.
As can be seen from fig. 2(b) and 2(d), as the deposition time becomes longer, the loading amount of iron phosphate in the control group and the experimental group tends to increase and then decrease, because the increase in the deposition time decreases the binding force of the active material to the current collector, and thus the deposition quality tends to decrease. As shown in fig. 2(d), the experimental group has a high deposition rate between 10-15min and high deposition kinetics, the loading amount of iron phosphate is the highest at 13min, and since the distance between the counter electrode and the current collector is difficult to be ensured to be consistent in the dispersion liquid, the loading amount of the active substance has a certain error, and the current collector cannot be completely deposited and covered at 13min of deposition, but the current collector can be completely and uniformly deposited and covered at 15min of deposition and enough loading amount of the active substance can be ensured, so that the deposition layer is prevented from falling off when the active substance loading is combined and the cut piece is cut, and the deposition time is selected to be 15min to prepare the positive electrode piece.
Example 4: analyzing the optimal deposition voltage for preparing the positive pole piece when the deposition time is 15min
1. FePO is reacted with 4 CNTs and CTAB were mixed in a ratio of 1: 1 to prepare a dispersion, and then the prepared dispersion was subjected to a deposition reaction under conditions of a deposition time of 15min and deposition voltages of 10V, 15V and 20V, respectively, and the rest was the same as in example 1.
2. And (3) analyzing the positive pole piece prepared in the step (1) by using a scanning electron microscope (Gemini 500).
As can be seen from fig. 4(a), the surface of the positive electrode plate prepared at a deposition voltage of 10V is relatively uneven, and pits and cracks occur due to uneven deposition caused by too low film quality; as can be seen from fig. 4(b), the surface of the prepared electrode plate is relatively flat when the deposition voltage is 15V, and the charged particles in the suspension are uniformly deposited on the surface of the current collector, so that the electrode plate has a good bonding effect; as can be seen from fig. 4(c), cracks were generated on the surface of the positive electrode sheet obtained at a deposition voltage of 20V, which was caused by internal stress generated by solvent evaporation.
In summary, the optimal parameters for preparing the positive electrode plate are that the deposition voltage is 15V and the deposition time is 15 min.
Example 5: analysis of different FePO 4 Influence of the CNTs and CTAB ratios on electrochemical Performance
1. Preparation of electrode sheet
FePO is reacted with 4 Preparing three groups of dispersion liquid by CNTs and CTAB according to different mass ratios, and marking the dispersion liquid as an experiment group I, an experiment group II and an experiment group III; FePO is reacted with 4 A dispersion was prepared at a concentration of 1g/L and labeled as a control group. FePO of experiment group one 4 CNTs and CTAB in a mass ratio of 10: 1; FePO of Experimental group two 4 CNTs and CTAB in a mass ratio of 2: 1; FePO of experiment group III 4 The mass ratio of CNTs to CTAB is 1: 1. FePO in Experimental group Dispersion 4 The concentration is 1g/L, then the sodium ion battery pole piece is prepared by respectively carrying out the first experiment group, the second experiment group, the third experiment group or the control group under the conditions of 15V deposition voltage and 15min deposition time, and the other preparation steps are the same as those of the example 1.
After weighing, the loading capacity of the electrode active material is obtained, and the loading capacity of the active material of the positive electrode plate prepared in the experiment group I, the experiment group II and the experiment group III is 1.44mg/cm 2 、1.97mg/cm 2 And 3.23mg/cm 2 From this, it is understood that the larger the amount of the electrode active material is, as the concentration of CTAB increases, the FePO is selected in accordance with factors such as the cost and the battery effect 4 And CNTs and CTAB are dispersed in a mass ratio of 1: 1 to prepare the positive pole piece.
Meanwhile, a scanning electron microscope (Gemini500) is adopted to analyze the structural morphology of the positive pole piece prepared in the first experiment group, the second experiment group and the third experiment group; and analyzing the carbon content of the anode electrode materials prepared in the experiment group I, the experiment group II and the experiment group III in the air by a thermo-gravimetric analyzer (TG 209F 3 Tarsus), wherein the testing temperature is 30-800 ℃, and the heating rate is 10 ℃/min.
As shown in FIGS. 5(a), (b) and (c), the concentration of CTAB in the dispersant was increased, and FePO was observed 4 Number of CNTs in a/CNT three-dimensional network structureAnd increased, which is illustrated in FePO 4 A more compact conductive network is formed therearound. As can be seen from FIGS. 5(d), (e), (f), the weight loss curve decreases when the temperature is 30-200 ℃; when the temperature is 200 ℃ and 500 ℃, the weight loss curve is relatively gently reduced; at a temperature of 500 ℃ and 700 ℃, the weight loss curve begins to decrease rapidly again. This is because the material itself contains water of crystallization and is subject to varying degrees of drying, such that the mass initially lost by the thermogravimetric curve is that of water in the material, but as the temperature continues to increase, the carbon in the material pyrolyses under air conditions. The carbon content of run one, run two and run three was 14.81 wt%, 15.85 wt% and 19.46 wt%, respectively, except for the weight loss due to the small amount of water in the material. In summary, as the concentration of dispersant CTAB increases, the spherical FePO deposited 4 More CNTs are wrapped around the particles and the conductive network structure formed is more compact.
In addition, scanning electron microscopy (Gemini500) is adopted to analyze the surface SEM appearance of the dried positive pole piece of the control group or the third experimental group.
Fig. 6(a), (b) are SEM topography images of the surface of the dried current collector of the control or experimental group, respectively. As shown in FIG. 6(a), FePO 4 The particles are uniform spherical, the particle size is 30-100nm, as shown in FIG. 6(b), CNTs and FePO are added by CTAB 4 Good binding, and CNTs in FePO 4 The particles are wound and coated to form a three-dimensional network structure.
2. Sodium ion half cell assembly and electrochemical performance testing
Respectively taking the electrode plates prepared by the experiment group I, the experiment group II, the experiment group III or the comparison group in the step 1 as positive electrodes, taking metal sodium as negative electrodes and taking 1mol/L NaClO 4 The solvent is Propylene Carbonate (PC) containing 5% fluoroethylene carbonate (FEC) as an electrolyte, and a sodium ion half cell is assembled. Constant current charge and discharge tests are respectively carried out on sodium ion half batteries assembled in experiment group I, experiment group II or experiment group III by adopting Wuhan blue electricity battery test system (CT3002AU) and Shenzhen Xinwei battery test system (CT-4008), and the rate capability of the batteries is testedAnd cycle performance.
(1) Testing rate performance of sodium ion half-cell
Different current densities of 10mA/g, 20mA/g, 50mA/g, 100mA/g, 200mA/g, 500mA/g and 1000mA/g are respectively set to test the rate capability of the sodium-ion half cell through a test system.
As can be seen from fig. 7, as the CTAB concentration of the dispersant increases, the sodium ion half-cell with a higher CTAB concentration at different current densities also has a higher average discharge capacity, and the half-cells prepared in the first experimental group, the second experimental group and the third experimental group have average discharge capacities of 53.1mAh/g, 122.4mAh/g and 139.9mAh/g at a current density of 10mA/g, respectively. The specific discharge capacity of the second experimental group under different current densities is 133.6, 84.9, 42.8, 20.7, 9.3, 3.5 and 1.2mAh/g, and the specific discharge capacity of the third experimental group under different current densities is 142.2, 115.8, 76.8, 59.5, 40.6, 18.8 and 8.6mAh/g, so that the rate capability of the battery is obviously improved after the concentration of CTAB is increased.
(2) Testing the cycle performance of sodium ion half-cells
Because the average discharge capacity value of the experiment group I is too small, the experiment group II and the experiment group III are selected for subsequent cycle tests. The sodium ion half-cells prepared in experiment group two and experiment group three were subjected to 500 cycle tests by the test system at a current density of 100 mA/g.
As shown in fig. 8, the capacity of the half-cell prepared under the lower concentration CTAB in the second experimental group after 500 cycles at the current density of 100mA/g is 40.4mAh/g, and the capacity retention rate is 39.5%; the first-turn coulombic efficiency of the half-cell prepared in the third experimental group is about 65%, the coulombic efficiency gradually rises to be close to 100% in the subsequent charging and discharging processes and is kept stable, the capacity is 53.0mAh/g after the half-cell is circulated for 500 turns under the current density of 100mA/g, and the capacity retention rate is 48.1%. Therefore, the experimental group III has more stable cycle performance, and the improvement of CTAB concentration indeed enhances the charge-discharge capacity and rate capability of the system electrode.
(3) Testing the Effect of CNTs on Battery Performance
And the third experimental group has more stable cycle performance, so that the third experimental group is selected for subsequent multiplying power test. And (3) carrying out magnification test on the sodium ion half-cell assembled by the positive pole pieces prepared in the third control group and the third experiment group by adopting a test system under the current density of 10mA/g and the voltage of 1.5-4.0V.
Fig. 9(a) and (b) are the charge and discharge curves of the sodium ion half-cell prepared in the control group or the experiment group three at the current density of 10mA/g, wherein 1, 2 and 3 are the charge and discharge curves of the first three circles, it can be seen from fig. 9(a) that the discharge capacity of the sodium ion half-cell without CNTs is very low, and it can be seen from fig. 9(b) that the discharge capacity of the sodium ion half-cell with CNTs added in the second circle can reach 142.0 mAh/g. Therefore, the compounding of the CNTs can obviously improve the FePO 4 The discharge capacity of (2).
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a positive pole piece of a sodium-ion battery is characterized by comprising the following steps:
step 1, mixing an electrode active substance, a conductive agent and a dispersing agent in water, wherein the dispersing agent is a water-soluble substance, stirring for 5-10min, and then carrying out ultrasonic treatment for 10-30min to obtain a dispersion liquid with the electrode active substance and the conductive agent uniformly distributed;
step 2, immersing a counter electrode and a current collector in the dispersion liquid prepared in the step 1, depositing a mixed substance formed by an electrode active substance, a conductive agent and a dispersing agent on the current collector under the conditions that the deposition voltage is 5-50V and the deposition time is 5-30min, then putting the deposited current collector into a vacuum oven, and drying for 8-12 h;
and 3, compacting the current collector dried in the step 2, and cutting the current collector into a circular positive pole piece.
2. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the electricity is generatedThe electrode active material is polyanionic compound, and comprises FePO 4 、NaFePO 4 、Na 2 FeP 2 O 7 、Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )、Na 3 V 2 (PO 4 ) 3 、Na 2 FePO 4 F。
3. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1 or 2, wherein the particle size range of the electrode active material is 30nm to 300 nm.
4. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the conductive agent is a carbon-based material, and the conductive agent comprises carbon nanotubes, graphene and conductive carbon black.
5. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the dispersant comprises cetyl trimethyl ammonium bromide, poly [1- [4- (3-carboxy-4-hydroxyphenylazo) benzenesulfonylamino ] ethane diyl, sodium salt ] and benzoic acid.
6. The preparation method of the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the mass ratio of the electrode active substance, the conductive agent and the dispersing agent is 200: (100-200): (20-200).
7. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the counter electrode is a platinum electrode, and the current collector comprises an aluminum foil, a stainless steel sheet, a zinc sheet and a copper sheet.
8. The preparation method of the positive pole piece of the sodium-ion battery as claimed in claim 1 or 7, wherein the counter electrode and the current collector are parallel to each other in the dispersion liquid and the distance is 18-22 mm.
9. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the deposition voltage in step 2 is 15V, and the deposition time is 15 min.
10. The preparation method of the positive pole piece of the sodium-ion battery as claimed in claim 1, wherein the temperature of the vacuum oven is 60-100 ℃, and the vacuum degree is less than 100 pa.
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| CN101210339A (en) * | 2006-12-27 | 2008-07-02 | 上海比亚迪有限公司 | Method for preparing battery electrode |
| CN105609709A (en) * | 2016-03-03 | 2016-05-25 | 陕西科技大学 | Preparation method of electrode plate of ion secondary battery |
| CN109004225A (en) * | 2018-08-01 | 2018-12-14 | 太仓斯迪克新材料科技有限公司 | A kind of anode slice of lithium ion battery and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101210339A (en) * | 2006-12-27 | 2008-07-02 | 上海比亚迪有限公司 | Method for preparing battery electrode |
| CN105609709A (en) * | 2016-03-03 | 2016-05-25 | 陕西科技大学 | Preparation method of electrode plate of ion secondary battery |
| CN109004225A (en) * | 2018-08-01 | 2018-12-14 | 太仓斯迪克新材料科技有限公司 | A kind of anode slice of lithium ion battery and its preparation |
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