CN116130776A - Positive electrode slurry of sodium ion battery and preparation method thereof - Google Patents
Positive electrode slurry of sodium ion battery and preparation method thereof Download PDFInfo
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- CN116130776A CN116130776A CN202310050403.6A CN202310050403A CN116130776A CN 116130776 A CN116130776 A CN 116130776A CN 202310050403 A CN202310050403 A CN 202310050403A CN 116130776 A CN116130776 A CN 116130776A
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- positive electrode
- ion battery
- sodium ion
- electrode slurry
- sodium
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 35
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims abstract description 34
- 239000000853 adhesive Substances 0.000 claims abstract description 19
- 230000001070 adhesive effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004576 sand Substances 0.000 claims abstract description 18
- 239000003292 glue Substances 0.000 claims abstract description 17
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 229910003321 CoFe Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000003801 milling Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a sodium ion battery positive electrode slurry and a preparation method thereof, firstly mixing sodium hexafluorophosphate with ethylene carbonate to prepare sodium hexafluorophosphate solution, and adding a positive electrode active material and the sodium hexafluorophosphate solution into a sand mill for sand milling; then adding the conductive agent and the additive into a solvent, and adding the adhesive after ultrasonic treatment to prepare conductive glue solution; and adding the prepared conductive glue solution into the pretreated positive electrode active material, continuing to sand, homogenizing, and finally adjusting the viscosity of the slurry to obtain the sodium ion battery positive electrode slurry. The invention adopts sodium hexafluorophosphate and ethylene carbonate to prepare low solid content solution, can effectively prevent the gel phenomenon from happening in the homogenizing process, the conductive agent and the additive are combined by non-covalent bond, the agglomeration of small particle conductive agent is avoided, the compatibility with the adhesive is also increased, the dispersibility of the conductive agent and the stability of conductive glue solution are improved, and the electrochemical performance of the sodium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of sodium ion battery manufacturing, in particular to sodium ion battery anode slurry and a preparation method thereof.
Background
Along with the rapid increase of lithium electricity demands in the fields of electric automobiles, energy storage and the like, lithium resources are more and more intense, lithium salt prices are also higher in water, and the emerging sodium ion batteries increasingly show advantages. Sodium is abundant in earth crust and widely distributed, the positive electrode of the sodium ion battery and the lithium ion battery have similar deintercalation mechanisms, the cycle performance of the lithium ion battery is comparable, and the low-temperature and low-rate performance of the lithium ion battery is superior, so that the positive electrode of the sodium ion battery becomes a new generation electrochemical system with huge potential.
The production process of the positive electrode of the sodium ion battery is similar to that of a lithium ion battery, and the positive electrode of the sodium ion battery can be produced by using the existing lithium ion battery production line, but the sodium ion battery is not produced in large scale at present, and a plurality of process problems are not solved. The sodium salt residues are generated after sintering of the sodium ion battery positive electrode material, particularly the layered transition metal oxide, so that the sodium ion battery positive electrode material is high in alkalinity, the positive electrode material is easy to absorb water in the process of homogenizing positive electrode slurry, the viscosity is increased in the process of homogenizing, jelly-shaped gel is easy to form, and the processing is difficult. In addition, in order to ensure better transmission performance of positive electrode active particle electrons, the super conductive carbon black with smaller particle size of carbon nano tubes or particles is generally selected, but the smaller particle size also causes poor dispersibility in positive electrode slurry, so that agglomeration among particles occurs in the homogenization process, and the electrochemical performance of the sodium ion battery is influenced. Based on the above research, it is necessary to provide a positive electrode slurry for sodium ion batteries and a preparation process thereof to meet the requirements.
Disclosure of Invention
The invention aims to solve the technical problem of providing the positive electrode slurry of the sodium ion battery and the preparation method thereof, which can effectively prevent the gel phenomenon in the homogenization process, improve the dispersibility of the conductive agent and the stability of the conductive adhesive solution, improve the electrochemical performance of the sodium ion battery, and have the advantages of excellent dispersion effect, good fluidity and stability and convenient processing.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: mixing sodium hexafluorophosphate with ethylene carbonate to prepare sodium hexafluorophosphate solution, adding the positive electrode active material and the sodium hexafluorophosphate solution into a sand mill, and sanding for 10-60 min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding a conductive agent and an additive into a solvent, performing ultrasonic treatment for 30-60 min, then adding an adhesive, and stirring at a speed of 800-1500 rpm for 1-3 h to obtain a conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (2) into the pretreated positive electrode active material prepared in the step (1), continuing to sand for 30-90 min, then transferring into a high-speed dispersing machine, adding a solvent, adjusting the revolution speed to 20-30 rpm, the autorotation speed to 1000-2000 rpm, starting the vacuum degree to-0.085-0.1 MPa, starting water cooling, keeping the temperature at 15-40 ℃, stirring for 30-180 min, and then adjusting the viscosity of the slurry to be qualified to obtain the positive electrode slurry of the sodium ion battery.
Preferably, the positive electrode active material is selected from Na 2 Zr 2 Si 2 PO 12 、Na 2/3 MnO 2 、Na 2/3 Mn 1/2 Fe 1/2 O 2 、Na 7/ 9 Cu 2/9 Mn 2/3 Fe 1/3 O 2 、Na 2 MnP 2 O 7 、Na 2 FeP 2 O 7 、Na 3 V 2 (PO 4 ) 3 、Na 2 MnFe(CN) 6 、Na 2 CoFe(CN) 6 At least one of them.
Preferably, the mass ratio of the sodium hexafluorophosphate to the ethylene carbonate in the step (1) is 1-3: 5 to 20.
Preferably, the sodium hexafluorophosphate in the step (1) accounts for 0.5 to 3% of the mass of the positive electrode active material. Preferably, the additive of step (2) has the formula
Wherein n=1 to 10.
Preferably, the mass of the additive in the step (2) accounts for 0.5-2% of the mass of the conductive agent; the mass ratio of the conductive agent to the adhesive is 1:1-2.
Preferably, the slurry viscosity in step (3) is adjusted to 4000-10000cp.
Preferably, the solid content of the conductive adhesive solution obtained in the step (2) is 5-15%.
The invention has the beneficial effects that:
the invention adopts sodium hexafluorophosphate and ethylene carbonate to prepare low solid content solution, then the solution is mixed with the positive electrode active material in a sand mill, the ethylene carbonate is used for dissolving sodium hexafluorophosphate on one hand, so that the sodium hexafluorophosphate can be fully contacted with the positive electrode active material, on the other hand, the toughness of a pole piece is improved by taking the sodium hexafluorophosphate as a plasticizer, and meanwhile, the sodium hexafluorophosphate can be used as Lewis acid to perform neutralization reaction with free alkali in the positive electrode active material, thereby effectively preventing gel phenomenon in the homogenizing process, and meanwhile, na with stable structure is generated by reaction 3 PO 4 And NaF, stabilize the positive electrode interface film, accelerate the diffusion of sodium ions; in addition, the conductive agent and the additive are combined in a non-covalent bond way, so that aggregation of the small-particle conductive agent is avoided, the compatibility of the small-particle conductive agent and the adhesive is also improved, the dispersibility of the conductive agent and the stability of the conductive adhesive solution are improved, and the electrochemical performance of the sodium ion battery is improved; in addition, the preparation process disclosed by the invention has the advantages of high production efficiency, excellent dispersion effect of the prepared slurry, good fluidity and stability and convenience in processing.
Detailed Description
The following examples are given to illustrate the invention in detail, but are not intended to limit the scope of the invention in any way. The equipment elements referred to in the following examples are conventional equipment elements unless otherwise specified; the industrial materials are commercially available conventional industrial materials unless otherwise specified.
Example 1: the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: 1g of sodium hexafluorophosphate was mixed with 10g of ethylene carbonate to prepare a sodium hexafluorophosphate solution, and then 95g of Na was added 3 V 2 (PO 4 ) 3 Adding the prepared sodium hexafluorophosphate solution into a sand mill, and sanding for 30min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding 2g of conductive carbon black and 0.02g of additive into 36g of N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, then adding 2g of polyvinylidene fluoride, and stirring at a speed of 1000rpm for 2h to obtain conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (II) into the pretreated positive electrode active material prepared in the step (I), continuing to sand for 60min, then transferring into a high-speed dispersing machine, adding 15g of N-methyl pyrrolidone, adjusting the revolution speed to 23rpm, the rotation speed to 2000rpm, the vacuum degree to-0.09 MPa, starting water cooling, keeping the temperature at 35 ℃ or less, stirring for 120min, and then adjusting the viscosity of the slurry to obtain the positive electrode slurry of the sodium ion battery.
Example 2: the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: 1.8g of sodium hexafluorophosphate was mixed with 10g of ethylene carbonate to prepare a sodium hexafluorophosphate solution, and 94.2g of Na 3 V 2 (PO 4 ) 3 Adding the prepared sodium hexafluorophosphate solution into a sand mill, and sanding for 30min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding 2g of conductive carbon black and 0.02g of additive into 50g of N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, then adding 2g of polyvinylidene fluoride, and stirring at a speed of 1000rpm for 2h to obtain conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (II) into the pretreated positive electrode active material prepared in the step (I), continuing to sand for 60min, then transferring into a high-speed dispersing machine, adding 15g of N-methyl pyrrolidone, adjusting the revolution speed to 23rpm, the rotation speed to 2000rpm, the vacuum degree to-0.09 MPa, starting water cooling, keeping the temperature at 35 ℃ or less, stirring for 120min, and then adjusting the viscosity of the slurry to obtain the positive electrode slurry of the sodium ion battery.
Example 3: the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: 1g of sodium hexafluorophosphate was mixed with 10g of ethylene carbonate to prepare a sodium hexafluorophosphate solution, and then 95g of Na was added 3 V 2 (PO 4 ) 3 Adding the prepared sodium hexafluorophosphate solution into a sand mill, and sanding for 30min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding 2g of conductive carbon black and 0.04g of additive into 50g of N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, then adding 2g of polyvinylidene fluoride, and stirring at a speed of 1000rpm for 2h to obtain conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (II) into the pretreated positive electrode active material prepared in the step (I), continuing to sand for 60min, then transferring into a high-speed dispersing machine, adding 15g of N-methyl pyrrolidone, adjusting the revolution speed to 23rpm, the rotation speed to 2000rpm, the vacuum degree to-0.09 MPa, starting water cooling, keeping the temperature at 35 ℃ or less, stirring for 120min, and then adjusting the viscosity of the slurry to obtain the positive electrode slurry of the sodium ion battery.
Example 4: the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: 1g of sodium hexafluorophosphate was mixed with 10g of ethylene carbonate to prepare a sodium hexafluorophosphate solution, and then 95g of Na was added 3 V 2 (PO 4 ) 3 Adding the prepared sodium hexafluorophosphate solution into a sand mill, and sanding for 30min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding 2g of conductive carbon black and 0.01g of additive into 50g of N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, then adding 2g of polyvinylidene fluoride, and stirring at a speed of 1000rpm for 2h to obtain conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (II) into the pretreated positive electrode active material prepared in the step (I), continuing to sand for 60min, then transferring into a high-speed dispersing machine, adding 15g of N-methyl pyrrolidone, adjusting the revolution speed to 23rpm, the rotation speed to 2000rpm, the vacuum degree to-0.09 MPa, starting water cooling, keeping the temperature at 35 ℃ or less, stirring for 120min, and then adjusting the viscosity of the slurry to obtain the positive electrode slurry of the sodium ion battery.
Example 5: the preparation method of the positive electrode slurry of the sodium ion battery comprises the following steps:
(1) Pretreatment of positive electrode active material: 1g of sodium hexafluorophosphate was mixed with 10g of ethylene carbonate to prepare a sodium hexafluorophosphate solution, and then 95g of Na was added 2 MnFe(CN) 6 Adding the prepared sodium hexafluorophosphate solution into a sand mill, and sanding for 30min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding 2g of conductive carbon black and 0.02g of additive into 36g of N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, then adding 2g of polyvinylidene fluoride, and stirring at a speed of 1000rpm for 2h to obtain conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (II) into the pretreated positive electrode active material prepared in the step (I), continuing to sand for 60min, then transferring into a high-speed dispersing machine, adding 15g of N-methyl pyrrolidone, adjusting the revolution speed to 23rpm, the rotation speed to 2000rpm, the vacuum degree to-0.09 MPa, starting water cooling, keeping the temperature at 35 ℃ or less, stirring for 120min, and then adjusting the viscosity of the slurry to obtain the positive electrode slurry of the sodium ion battery.
Comparative example 1: 96g of Na 3 V 2 (PO 4 ) 3 Adding 2g of conductive carbon black and 2g of polyvinylidene fluoride into a double planetary stirrer, setting the revolution speed to be 23rpm, stirring for 30min, then adding 61g of N-methylpyrrolidone, setting the revolution speed to be 23rpm, and rotating at a speed2000rpm, the vacuum degree is-0.09 MPa, water cooling is started, the temperature is kept to be less than or equal to 35 ℃, stirring is carried out for 120min, then the viscosity of the slurry is regulated, and the sodium ion battery anode slurry is obtained after the viscosity is qualified.
The positive electrode slurries of sodium ion batteries prepared in examples 1 to 5 and comparative example 1 were tested for the electrode sheet resistance and 100-cycle capacity retention, and the test results are shown in table 1 below.
Table 1 positive electrode slurry test results of sodium ion batteries prepared in examples 1 to 5 and comparative example 1
From the detection results, the positive electrode slurry of the sodium ion battery prepared by the method has the advantages that no gel phenomenon occurs in the homogenizing process, the impedance rate of the pole piece is low, the current utilization rate is high, the 100-cycle capacity retention rate can reach more than 88 percent and can reach 93.90 percent, and the electrochemical performance of the sodium ion battery of the positive electrode slurry of the sodium ion battery prepared by the method is effectively improved.
While the invention has been described with reference to the embodiments, those skilled in the art will understand that various specific parameters in the above embodiments may be changed without departing from the spirit of the invention, and thus a plurality of specific embodiments are common variation ranges of the invention, and will not be described in detail herein.
Claims (10)
1. The preparation method of the positive electrode slurry of the sodium ion battery is characterized by comprising the following steps of:
(1) Pretreatment of positive electrode active material: mixing sodium hexafluorophosphate with ethylene carbonate to prepare sodium hexafluorophosphate solution, adding the positive electrode active material and the sodium hexafluorophosphate solution into a sand mill, and sanding for 10-60 min to obtain a pretreated positive electrode active material;
(2) Preparing conductive glue solution: adding a conductive agent and an additive into a solvent, performing ultrasonic treatment for 30-60 min, then adding an adhesive, and stirring at a speed of 800-1500 rpm for 1-3 h to obtain a conductive glue solution;
(3) Preparing positive electrode slurry: adding the conductive adhesive solution prepared in the step (2) into the pretreated positive electrode active material prepared in the step (1), continuing to sand for 30-90 min, then transferring into a high-speed dispersing machine, adding a solvent, adjusting the revolution speed to 20-30 rpm, the autorotation speed to 1000-2000 rpm, starting the vacuum degree to-0.085-0.1 MPa, starting water cooling, keeping the temperature at 15-40 ℃, stirring for 30-180 min, and then adjusting the viscosity of the slurry to be qualified to obtain the positive electrode slurry of the sodium ion battery.
2. The method for preparing a positive electrode slurry for sodium ion battery according to claim 1, wherein the positive electrode active material in the step (1) is selected from Na 2 Zr 2 Si 2 PO 12 、Na 2/3 MnO 2 、Na 2/3 Mn 1/2 Fe 1/2 O 2 、Na 7/9 Cu 2/9 Mn 2/3 Fe 1/3 O 2 、Na 2 MnP 2 O 7 、Na 2 FeP 2 O 7 、Na 3 V 2 (PO 4 ) 3 、Na 2 MnFe(CN) 6 、Na 2 CoFe(CN) 6 At least one of them.
3. The method for preparing the sodium ion battery positive electrode slurry according to claim 1, wherein the mass ratio of the sodium hexafluorophosphate to the ethylene carbonate in the step (1) is 1-3: 5 to 20.
4. The method for preparing a sodium ion battery positive electrode slurry according to claim 1, wherein the mass of the sodium hexafluorophosphate in the step (1) is 0.5-3% of the mass of the positive electrode active material.
5. The method for preparing a positive electrode slurry for sodium ion battery according to claim 1, wherein the additive in the step (2) has a structural formula of
Wherein n=1 to 10.
6. The method for preparing a sodium ion battery positive electrode slurry according to claim 1, wherein the conductive agent in the step (2) is conductive carbon black; the solvent is N-methyl pyrrolidone; the adhesive is polyvinylidene fluoride.
7. The method for preparing the positive electrode slurry of the sodium ion battery according to claim 1, wherein the mass of the additive in the step (2) accounts for 0.5-2% of the mass of the conductive agent; the mass ratio of the conductive agent to the adhesive is 1:1-2.
8. The method for preparing a sodium ion battery positive electrode slurry according to claim 1, wherein the viscosity of the slurry in the step (3) is adjusted to 4000-10000cp.
9. The method for preparing the positive electrode slurry of the sodium ion battery according to claim 1, wherein the solid content of the conductive adhesive solution obtained in the step (2) is 5-15%.
10. A sodium ion battery positive electrode slurry prepared by the preparation method of any one of claims 1 to 7.
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| CN116487594A (en) * | 2023-06-14 | 2023-07-25 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and electric equipment |
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| CN116487594A (en) * | 2023-06-14 | 2023-07-25 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and electric equipment |
| CN116487594B (en) * | 2023-06-14 | 2024-01-23 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and electric equipment |
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