CN113161511A - Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof - Google Patents
Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN113161511A CN113161511A CN202110424569.0A CN202110424569A CN113161511A CN 113161511 A CN113161511 A CN 113161511A CN 202110424569 A CN202110424569 A CN 202110424569A CN 113161511 A CN113161511 A CN 113161511A
- Authority
- CN
- China
- Prior art keywords
- electrode
- ion battery
- battery
- plastic
- aqueous sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
-
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a plastic electrode and a preparation method thereof, and a water-system sodium-ion battery and a preparation method thereof, wherein the preparation method of the plastic electrode comprises the following steps: mixing electrolyte salt and deionized water to form electrolyte solution; adding a surfactant and a humectant into an electrolyte solution, and mixing to form a uniform solvent matrix; adding a conductive material into a solvent matrix, and uniformly dispersing the conductive material in the solvent matrix; adding a positive/negative electrode active material and a binder; adding a cross-linking agent, stirring and mixing at a low speed, and carrying out cross-linking action with the binder to form the aqueous sodium-ion battery plastic electrode paste with a three-dimensional network structure. The plasticity electrode is a stable mixture of active substances and electrolyte, the electrolyte is locked in the plasticity electrode, the ion diffusion path is reduced during charging and discharging of the battery, the ionic impedance and the electronic impedance are greatly reduced, and the high-rate output is facilitated; the preparation of the electrode and the assembly of the battery are completed synchronously, the liquid injection process is omitted, and the preparation process of the battery is simplified.
Description
Technical Field
The invention belongs to the field of water-based battery materials, and particularly relates to a plastic electrode and a preparation method thereof, a water-based sodium ion battery and a preparation method thereof.
Background
Resource-based fossil fuels have remained a major source of human power to date. Carbon emission caused by the heavy use of the carbon is a main cause of the current global warming effect. Intermittent renewable energy sources, represented by solar and wind energy, must be connected to the grid through the storage and release of energy storage systems. Therefore, the large-scale energy storage technology is the basis of new energy popularization and energy innovation, is an important component of national energy strategic demand layout, and has important effects on national energy structure optimization and safe and stable operation of a power grid. Due to the advantages of high conversion efficiency, flexible assembly, no geographical environment constraint and the like, the electrochemical cell becomes a research hotspot of energy storage technology, and the application is gradually commercialized from demonstration. The development of lithium ion batteries based on organic electrolytes is quite mature, and the lithium ion batteries are widely applied to mobile electronic equipment, electric vehicles and various high-specific energy scenes. However, the energy storage application of large-scale integration (above MWh level) has the characteristics of large investment, long operation and maintenance period and the like, and is influenced by the consistency of batteries, difficult control of integration scale and the like, and a series of combustion accidents of energy storage systems and power stations occur in the world in recent years, which shows that the intrinsic safety of the batteries still needs to be paid high attention, and is also a difficult problem which needs to be solved urgently in the large-scale popularization of the energy storage batteries at present.
The water system ion battery adopts neutral saline solution as electrolyte, which not only avoids the flammability problem of organic electrolyte, but also overcomes the defects of high pollution, short service life (such as lead-acid battery) and high price (nickel-hydrogen battery) of the traditional water system battery, has the characteristics of safety, low cost, long service life, environmental protection, recyclability and the like, is a brand new novel battery, and is an ideal system with large-scale energy storage technical requirements. Among them, the aqueous sodium ion battery is one of the most investment potential energy storage batteries. The development of the water-based sodium-ion battery as a brand-new battery also has certain challenges, such as the gram capacity of the battery is lower than that of other existing batteries, and a thick electrode (the thickness is more than 1.0 mm) is required to improve the specific energy of the battery. Therefore, in the existing mature electrode manufacturing process, the coating of the lithium battery or the slurry drawing process of the nickel-metal hydride battery can only prepare a thinner pole piece, and the production of the thick pole piece of the water system sodium-ion battery cannot be finished.
Patent CN104871349A mentions that the aqueous sodium ion battery is formed by sequentially stacking and assembling sheet square electrodes, the sheet electrodes are formed by pressing a mixture of active materials, conductive agents and binders, the development of large-area electrodes is limited by the large aspect ratio (ratio of side length to thickness) of the sheet electrodes, so that a single cell contains hundreds of electrodes, and the uniformity of the product in size and performance is difficult to ensure due to the interference of multiple factors such as different proficiencies of equipment and actual operators, and the arrangement of multiple electrodes makes the battery assembly extremely complex, thereby affecting the electrochemical performance and service life of the battery, and thus limiting the engineering application thereof.
Patent CN 109351793A mentions a pole piece extrusion device and system, active material is coated on the current collector after extrusion molding to form the pole piece. The system consists of two major parts, namely active substance forming and electrode plate compounding, and relates to preparation processes of active substance mixing, kneading, conveying and the like, and processes of decoiling of a current collector, coating of an electrode plate, drying, compacting, rolling and the like. Each process procedure can cause certain uncontrollable influence on the performance of the actual product, and the complicated preparation process seriously reduces the controllability of the product, thereby influencing the performance of the battery.
Disclosure of Invention
The invention aims to provide a plastic electrode of a water system sodium ion battery, aiming at the problems of complex production and assembly, poor process controllability, poor battery performance consistency and the like of the existing water system sodium ion battery in the background technology.
The technical scheme of the invention is as follows: a plasticity electrode of a water system sodium-ion battery comprises the following components in percentage by mass: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
Further, the positive/negative active material is a positive electrode active material in the positive electrode and a negative electrode active material in the negative electrode, and the positive electrode active material includes but is not limited to at least one of transition metal oxide, phosphate polyanion compound, prussian blue analogue or organic electrode material; the negative active material includes but is not limited to at least one of activated carbon, Prussian blue analogue, sodium storage organic matter and titanium phosphorus-based oxide.
Further, the conductive material includes, but is not limited to, at least one of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber, and mesoporous carbon.
Further, the binder includes, but is not limited to, at least one of polyacrylic acid, polyvinyl alcohol, antler pectin, hydroxyethyl cellulose, xanthan gum, polytetrafluoroethylene, and PVDF.
Further, the cross-linking agent includes but is not limited to at least one of a silane cross-linking agent, polyvinyl alcohol, and boric acid, and the humectant includes but is not limited to at least one of glycerin, sorbitol, propylene glycol, and polyethylene glycol.
Further, the surfactant includes, but is not limited to, at least one of sodium dodecyl benzene sulfonate and stearic acid.
Further, the electrolyte salt includes, but is not limited to, at least one of sodium sulfate, sodium nitrate, sodium hypochlorite and sodium sulfite.
The second invention aims to provide a preparation method of a plasticity electrode of an aqueous sodium-ion battery, which comprises the following steps: s1, uniformly mixing electrolyte salt and deionized water to form electrolyte solution;
s2, adding the surfactant and the humectant into the electrolyte solution, and mixing to form a uniform solvent matrix;
s3, adding the conductive material into the solvent matrix, and uniformly dispersing the conductive material in the solvent matrix by high-speed stirring;
s4, if preparing a positive electrode, adding a positive active material and a binder, if preparing a negative electrode, adding a negative active material and a binder, and then stirring at a high speed and mixing uniformly;
s5, adding a cross-linking agent, stirring and mixing at a low speed, and enabling the cross-linking agent and the binder to generate a cross-linking effect to form a three-dimensional network-structured aqueous sodium-ion battery plastic electrode paste;
in the preparation steps, the weight percentages of the components are as follows: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
A third object of the present invention is to provide a method for producing an aqueous sodium ion battery, comprising: which comprises the following steps: z1 placing a lower splint and then placing a lower current collector on the lower splint;
z2 placing a conductive plate on the lower current collector, and adding a proper amount of negative plastic electrode paste on the conductive plate;
z3 placing a diaphragm on the negative electrode plastic electrode paste, and pre-pressing and shaping the negative electrode plastic electrode paste;
z4 adding a proper amount of positive plastic electrode paste on the diaphragm;
z5 repeating the steps Z2-Z4 for a plurality of times until the number of electrode layers required by the battery design capacity is completed, and pre-pressing and shaping the positive plastic electrode paste body when placing the conductive plate each time;
z6 sequentially placing an upper conductive plate, an upper current collector and an upper clamping plate to prepare the plastic electrode aqueous sodium ion battery.
The invention also provides a water system sodium ion battery, which sequentially comprises a lower clamping plate, a lower current collector, a current conducting plate, a negative electrode plastic electrode, a diaphragm, a positive electrode plastic electrode, an upper current conducting plate, an upper current collector and an upper clamping plate from bottom to top, wherein a plurality of battery units consisting of the current conducting plate, the negative electrode plastic electrode, the diaphragm and the positive electrode plastic electrode are arranged between the lower clamping plate and the upper current conducting plate, upward convex edges are arranged on two sides of the current conducting plate and the diaphragm, the height of the convex edge on the current conducting plate corresponds to the thickness of the negative electrode plastic electrode, the height of the convex edge of the diaphragm corresponds to the thickness of the positive electrode plastic electrode, and the lower clamping plate, the lower current collector, the upper current conducting plate, the upper current collector and the upper clamping plate are plate-shaped parts.
The invention has the beneficial effects that: 1) the water system sodium ion battery plasticity electrode is a stable mixture of active substances and electrolyte, the electrolyte is locked by the plasticity electrode, the ion diffusion path is greatly reduced in the battery charging and discharging process, the ionic impedance and the electronic impedance are greatly reduced, and the high-rate output is facilitated; 2) the design of the plasticity electrode of the water system sodium ion battery breaks through the limitation of a sheet electrode, and the electrode with any size and any shape can be prepared, so that batteries/modules with different shapes can be obtained, the requirements of different customers on the appearance of the battery are met, or the product is customized; 3) according to the preparation method of the water system sodium ion battery, the preparation of the electrode and the assembly of the battery are completed synchronously, and the liquid injection process is omitted in the assembly process, so that the preparation flow of the battery is greatly reduced; 4) the aqueous sodium ion battery prepared by the preparation method of the aqueous sodium ion battery has no corrosion of a metal current collector, and can be circulated for a long service life; 4) the aqueous sodium ion battery has greatly improved production flexibility, and can be used for deploying products with various floor areas, charge and discharge rates and energy.
Drawings
Fig. 1 is a schematic view of a process flow for preparing an aqueous sodium-ion battery according to the present invention.
Fig. 2 is a schematic view of the structure of an aqueous sodium-ion battery according to the present invention.
Fig. 3 is a graph of the sodium ion cycle performance data of the water system prepared in the application example.
Fig. 4 is an external view of an aqueous sodium ion battery in an application example.
Fig. 5 is a block diagram of a battery disposed within a wall interlayer.
Labeled as: the device comprises a lower clamping plate 1, a lower current collector 2, a conducting plate 3, a negative electrode plastic electrode 4, a diaphragm 5, a positive electrode plastic electrode 6, an upper conducting plate 7, an upper current collector 8, an upper clamping plate 9, a wall interlayer 10 and a battery 11.
Detailed Description
The invention is further described below with reference to the figures and examples.
A plasticity electrode of a water system sodium-ion battery comprises the following components in percentage by mass: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
The positive electrode active material includes, but is not limited to, at least one of transition metal oxide, phosphate polyanion compound, prussian blue analog, or organic electrode material. Transition metal oxides include, but are not limited to, MnO2，NaxMnO2B, carrying out the following steps of; phosphate polyanionic compounds include, but are not limited to, Na3V2(PO4)3, NaFePO4, NaVPO4F; prussian blue analogs include, but are not limited to, Na2NiFe(CN)6, KCo0.5Cu0.5Fe(CN)6(ii) a Organic electrode materials include, but are not limited to, poly 2, 2, 6, 6-tetramethylpiperidinyloxy-4-vinyl ether (PTVE).
The negative active material includes but is not limited to at least one of activated carbon, Prussian blue analogue, sodium storage organic matter and titanium phosphorus-based oxide. Prussian blue analogs include, but are not limited to, K0.11Mn[Mn(CN)6]0.83·3.64H2O; sodium-storing organics include, but are not limited to, polyimides, anthraquinone-structured polymers, disodium naphthalene dicarboxylate, and the like; titanium phosphorus-based oxides include, but are not limited to, NaTi2(PO4)3, NaV3(PO4)3，Na2VTi(PO4)3And the like.
The conductive material includes, but is not limited to, at least one of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber, and mesoporous carbon.
The binder includes, but is not limited to, at least one of polyacrylic acid, polyvinyl alcohol, pectin, hydroxyethyl cellulose, xanthan gum, polytetrafluoroethylene, PVDF.
The crosslinking agent includes but is not limited to at least one of silane crosslinking agent, polyvinyl alcohol, boric acid.
The humectant includes, but is not limited to, at least one of glycerin, sorbitol, propylene glycol, and polyethylene glycol.
The surfactant includes but is not limited to at least one of sodium dodecyl benzene sulfonate and stearic acid.
The electrolyte salt includes, but is not limited to, at least one of sodium sulfate, sodium nitrate, sodium hypochlorite, and sodium sulfite.
A preparation method of a water system sodium-ion battery plastic electrode comprises the following steps: s1, uniformly mixing electrolyte salt and deionized water to form electrolyte solution;
s2, adding the surfactant and the humectant into the electrolyte solution, and mixing to form a uniform solvent matrix;
s3, adding the conductive material into the solvent matrix, and uniformly dispersing the conductive material in the solvent matrix by high-speed stirring;
s4, if preparing a positive electrode, adding a positive active material and a binder, if preparing a negative electrode, adding a negative active material and a binder, and then stirring at a high speed and mixing uniformly;
s5, adding a cross-linking agent, stirring and mixing at a low speed, and enabling the cross-linking agent and the binder to generate a cross-linking effect to form a three-dimensional network-structured aqueous sodium-ion battery plastic electrode paste;
in the preparation steps, the weight percentages of the components are as follows: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
A method of aqueous sodium ion battery comprising the steps of: z1 placing a lower splint and then placing a lower current collector on the lower splint;
z2 placing a conductive plate on the lower current collector, and adding a proper amount of negative plastic electrode paste on the conductive plate;
z3 placing a diaphragm on the negative electrode plastic electrode paste, and pre-pressing and shaping the negative electrode plastic electrode paste;
z4 adding a proper amount of positive plastic electrode paste on the diaphragm;
z5 repeating the steps Z2-Z4 for a plurality of times until the number of electrode layers required by the battery design capacity is completed, and pre-pressing and shaping the positive plastic electrode paste body when placing the conductive plate each time;
z6 sequentially placing an upper conductive plate, an upper current collector and an upper clamping plate to prepare the plastic electrode aqueous sodium ion battery.
The utility model provides a river system sodium ion battery, from the bottom up includes lower plate, lower current collector, current conducting plate, negative pole plasticity electrode, diaphragm, anodal plasticity electrode in proper order, goes up the current conducting plate, goes up current collector and punch holder, is equipped with the battery cell that a plurality of groups current conducting plate, negative pole plasticity electrode, diaphragm, anodal plasticity electrode are constituteed between lower plate and last current conducting plate, the both sides of current conducting plate and diaphragm all be equipped with upwards protruding edge, the height on the current conducting plate of protruding edge is corresponding with the thickness of negative pole plasticity electrode, the height on the protruding edge of diaphragm is corresponding with the thickness of anodal plasticity electrode, lower plate, lower current collector, last current conducting plate, last current collector and punch holder all are platelike spare.
The upper clamping plate and the lower clamping plate are made of any plate materials capable of bearing pressure, such as stainless steel, plastics and the like. The upper current collector and the lower current collector are Cu, Al or stainless steel. The diaphragm is porous non-woven fabrics such as PP, PC and the like. The conducting plate is made of non-porous and waterproof conducting materials: the first scheme is that conductive carbon materials (graphite, carbon black, acetylene black and the like) and plastic matrixes (PE, PP and the like) are mixed and are made into a membrane with the thickness of 0.3-2mm by processes of extrusion, blow molding and the like; the second scheme is that the porous graphite paper/board is dipped to obtain non-porous and waterproof dipped graphite paper/board; in the third scheme, the low molecular weight polyethylene (LDPE) plugs the hollow of the graphite paper in a hot pressing mode to obtain the waterproof graphite paper.
The positive electrode plastic electrode and the negative electrode plastic electrode are pasty plastic electrodes prepared by the materials and the process.
Application example
A plasticity electrode of water system Na-ion battery, the positive electrode active material adopts Na0.44MnO2Negative electrode active materialSelecting sodium titanium phosphate, selecting a mixed conductive agent of graphite and acetylene black as a conductive material, wherein the mass ratio of the graphite to the acetylene black is 1: 1, polyvinyl alcohol is selected as a binder, borax is selected as a crosslinking agent, polyethylene glycol is selected as a humectant, sodium dodecyl benzene sulfonate is selected as a surfactant, and sodium sulfate is selected as an electrolyte salt.
The preparation method of the plastic electrode comprises the following steps: s1 sodium sulfate and deionized water are mixed to prepare 1M/L electrolyte solution; s2, adding sodium dodecyl benzene sulfonate (the mass ratio of the sodium dodecyl benzene sulfonate to the electrolyte solution is 1%) and polyethylene glycol (the mass ratio of the polyethylene glycol to the electrolyte solution is 2%) into the electrolyte solution to prepare a uniform solvent matrix; s3, adding a conductive carbon material (the mass ratio of the conductive carbon material to the active substance is 8: 85) into the uniformly mixed solvent matrix, and uniformly dispersing the carbon material in the solvent matrix by high-speed stirring (1000 RMP); s4, adding a positive/negative electrode active material and a binder (the mass ratio of the positive/negative electrode active material to the active material is 5: 85), and stirring at a high speed and mixing uniformly; s5, adding a cross-linking agent (the mass ratio of the cross-linking agent to the active substance is 2: 85), stirring at a low speed (100 RMP), and mixing to enable the cross-linking agent and the binder to generate a three-dimensional network structure;
in the above scheme, the ratio of the mass of the positive/negative electrode active material, the binder, and the crosslinking agent to the mass of the solvent base is 70: 30.
the plastic electrode can be used for preparing an aqueous sodium-ion battery.
As shown in fig. 5, the battery can be designed as an indoor sandwich type energy storage battery, and placed in the interlayer of the wall, the battery is in a strip shape and long: width: the height ratio is 10: 1: 5.
the water system sodium ion battery is prepared by adopting the plastic electrode according to the process steps shown in figure 1, and the specific steps are as follows: s1, sequentially placing a lower clamping plate and a lower fluid collector; s2, placing a conductive plate on the lower current collector, and adding a proper amount of negative plastic electrode paste on the conductive plate; s3, placing a diaphragm on the negative electrode plastic electrode paste, and pre-pressing and shaping the negative electrode plastic electrode paste; s4, adding a proper amount of positive plastic electrode paste on the diaphragm; s5, repeating the steps S2-S4 for a plurality of times until the number of electrode layers required by the design capacity of the battery is completed, and pre-pressing and shaping the positive plastic electrode paste body when a conductive plate is placed each time; s6, sequentially placing an upper conductive plate, an upper current collector and an upper clamping plate to obtain the plastic electrode aqueous sodium ion battery.
In the above scheme, ABS plastics can be chooseed for use to the splint, and the mass flow body can choose for use the stainless steel, and impregnated graphite plate can be chooseed for use to the current-conducting plate, and PP porous non-woven fabrics can be chooseed for use to the diaphragm.
Fig. 2 is a schematic structural diagram of the aqueous sodium ion battery of the present invention, which sequentially includes, from bottom to top, a lower clamping plate, a lower current collector, a current-conducting plate, a negative plastic electrode, a diaphragm, a positive plastic electrode, an upper current-conducting plate, an upper current collector, and an upper clamping plate, wherein a battery unit composed of a plurality of sets of current-conducting plates, negative plastic electrodes, diaphragms, and positive plastic electrodes is disposed between the lower clamping plate and the upper current-conducting plate, both sides of the current-conducting plate and the diaphragm are provided with upward convex edges, the height of the convex edge on the current-conducting plate corresponds to the thickness of the negative plastic electrode, the height of the convex edge of the diaphragm corresponds to the thickness of the positive plastic electrode, and the lower clamping plate, the lower current collector, the upper current-conducting plate, the upper current collector, and the upper clamping plate are plate-shaped members.
As shown in fig. 3, the obtained data graph of the cycling performance of the aqueous sodium ion shows that the capacity retention rate of the prepared aqueous sodium ion battery can still reach more than 85% after the prepared aqueous sodium ion battery is cycled for more than 6000 times.
The water system sodium ion battery can be produced in batch on a flow production line, the production flexibility is greatly improved, products with various occupied areas, charge and discharge rates and energy can be deployed, and the shape of the battery can be designed according to the application environment.
The above description is only for the preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes and substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A plasticity electrode of a water system sodium-ion battery is characterized in that: the composite material comprises the following components in percentage by mass: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
2. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the positive/negative active material is a positive electrode active material in the positive electrode and a negative electrode active material in the negative electrode, and the positive electrode active material comprises at least one of transition metal oxide, phosphate polyanion compound, Prussian blue analogue or organic electrode material; the negative active material includes but is not limited to at least one of activated carbon, Prussian blue analogue, sodium storage organic matter, titanium phosphorus-based oxide.
3. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the conductive material includes, but is not limited to, at least one of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber, and mesoporous carbon.
4. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the binder includes but is not limited to at least one of polyacrylic acid, polyvinyl alcohol, antler pectin, hydroxyethyl cellulose, xanthan gum, polytetrafluoroethylene and PVDF.
5. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the crosslinking agent includes but is not limited to at least one of silane crosslinking agent, polyvinyl alcohol and boric acid; the humectant includes but is not limited to at least one of glycerin, sorbitol, propylene glycol, and polyethylene glycol.
6. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the surfactant includes but is not limited to at least one of sodium dodecyl benzene sulfonate and stearic acid.
7. The aqueous sodium-ion battery plastic electrode and the battery manufacturing method according to claim 1, characterized in that: the electrolyte salt includes, but is not limited to, at least one of sodium sulfate, sodium nitrate, sodium hypochlorite, and sodium sulfite.
8. A preparation method of a water system sodium-ion battery plasticity electrode is characterized by comprising the following steps: which comprises the following steps: s1, uniformly mixing electrolyte salt and deionized water to form electrolyte solution;
s2, adding the surfactant and the humectant into the electrolyte solution, and mixing to form a uniform solvent matrix;
s3, adding the conductive material into the solvent matrix, and uniformly dispersing the conductive material in the solvent matrix by high-speed stirring;
s4, if preparing a positive electrode, adding a positive active material and a binder, if preparing a negative electrode, adding a negative active material and a binder, and then stirring at a high speed and mixing uniformly;
s5, adding a cross-linking agent, stirring and mixing at a low speed, and enabling the cross-linking agent and the binder to generate a cross-linking effect to form a three-dimensional network-structured aqueous sodium-ion battery plastic electrode paste;
in the preparation steps, the weight percentages of the components are as follows: 40-50% of positive/negative electrode active material, 3-10% of conductive material, 0-10% of binder, 0-5% of cross-linking agent, 0-10% of humectant, 0-3% of surfactant, 0-30% of electrolyte salt and 10-30% of deionized water.
9. A method for producing an aqueous sodium-ion battery using a plastic electrode according to any one of claims 1 to 8, characterized in that: which comprises the following steps: z1 placing a lower splint and then placing a lower current collector on the lower splint;
z2 placing a conductive plate on the lower current collector, and adding a proper amount of negative plastic electrode paste on the conductive plate;
z3 placing a diaphragm on the negative electrode plastic electrode paste, and pre-pressing and shaping the negative electrode plastic electrode paste;
z4 adding a proper amount of positive plastic electrode paste on the diaphragm;
z5 repeating the steps Z2-Z4 for a plurality of times until the number of electrode layers required by the battery design capacity is completed, and pre-pressing and shaping the positive plastic electrode paste body when placing the conductive plate each time;
z6 sequentially placing an upper conductive plate, an upper current collector and an upper clamping plate to prepare the plastic electrode aqueous sodium ion battery.
10. An aqueous sodium-ion battery characterized in that: from the bottom up includes lower plate, lower current collector, current conducting plate, negative pole plasticity electrode, diaphragm, anodal plasticity electrode in proper order, goes up the current conducting plate, goes up current collector and punch holder, is equipped with the battery unit that a plurality of groups current conducting plate, negative pole plasticity electrode, diaphragm, anodal plasticity electrode are constituteed between lower plate and last current conducting plate, the both sides of current conducting plate and diaphragm all be equipped with the protruding edge that makes progress, the height on the protruding edge on the current conducting plate is corresponding with the thickness of negative pole plasticity electrode, the height on the protruding edge of diaphragm is corresponding with the thickness of anodal plasticity electrode, lower plate, lower current collector, go up the current conducting plate, go up current collector and punch holder and all be platelike spare.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110424569.0A CN113161511B (en) | 2021-04-20 | 2021-04-20 | Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110424569.0A CN113161511B (en) | 2021-04-20 | 2021-04-20 | Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113161511A true CN113161511A (en) | 2021-07-23 |
| CN113161511B CN113161511B (en) | 2022-04-29 |
Family
ID=76869299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110424569.0A Active CN113161511B (en) | 2021-04-20 | 2021-04-20 | Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113161511B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367772A (en) * | 2022-09-15 | 2022-11-22 | 中国石油大学(华东) | Preparation method of prussian blue positive electrode material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116885268A (en) * | 2022-08-24 | 2023-10-13 | 太仓中科赛诺新能源科技有限公司 | Prussian blue analogue positive electrode material and electrochemical energy storage device |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040157130A1 (en) * | 2003-01-28 | 2004-08-12 | Nissan Motor Co., Ltd. | Electrode for secondary battery having gel polymer electrolyte, method of producing the same, and secondary battery |
| KR20100086689A (en) * | 2009-01-23 | 2010-08-02 | 에너그린(주) | Nickel-metal hydride secondary battery comprising cathode, anode or separator surface-modified with gel electrolyte for coating |
| WO2010087146A1 (en) * | 2009-01-30 | 2010-08-05 | 川崎重工業株式会社 | Alkaline rechargeable battery and binder for electrodes of alkaline rechargeable batteries |
| CN104600243A (en) * | 2015-01-28 | 2015-05-06 | 清华大学深圳研究生院 | Pole piece, energy storage device and preparation method of pole piece |
| CN104916809A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院金属研究所 | Integrated flexible electrode |
| US20180076481A1 (en) * | 2015-05-28 | 2018-03-15 | Fujifilm Corporation | Solid electrolyte composition, mixture, complexed gel, electrode sheet for all-solid state secondary battery, all-solid state secondary battery, and methods for manufacturing solid electrolyte composition, complexed gel, electrode sheet for all-solid state secondary battery and all-solid state secondary battery |
| CN107834106A (en) * | 2017-11-13 | 2018-03-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of flexible water system sodium-ion battery |
| US9960451B1 (en) * | 2017-05-24 | 2018-05-01 | Nanotek Instruments, Inc. | Method of producing deformable quasi-solid electrode material for alkali metal batteries |
| CN108075181A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of solid-state or colloidal state water-system alkali metal ion battery and preparation method thereof |
| CN111196888A (en) * | 2020-01-06 | 2020-05-26 | 浙江大学 | Gel polymer electrolyte doped with modified particles and preparation method and application thereof |
| CN111916850A (en) * | 2020-08-04 | 2020-11-10 | 太仓中科赛诺新能源科技有限公司 | Preparation method and structure of water system quasi-solid sodium ion battery |
-
2021
- 2021-04-20 CN CN202110424569.0A patent/CN113161511B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040157130A1 (en) * | 2003-01-28 | 2004-08-12 | Nissan Motor Co., Ltd. | Electrode for secondary battery having gel polymer electrolyte, method of producing the same, and secondary battery |
| KR20100086689A (en) * | 2009-01-23 | 2010-08-02 | 에너그린(주) | Nickel-metal hydride secondary battery comprising cathode, anode or separator surface-modified with gel electrolyte for coating |
| WO2010087146A1 (en) * | 2009-01-30 | 2010-08-05 | 川崎重工業株式会社 | Alkaline rechargeable battery and binder for electrodes of alkaline rechargeable batteries |
| CN104916809A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院金属研究所 | Integrated flexible electrode |
| CN104600243A (en) * | 2015-01-28 | 2015-05-06 | 清华大学深圳研究生院 | Pole piece, energy storage device and preparation method of pole piece |
| US20180076481A1 (en) * | 2015-05-28 | 2018-03-15 | Fujifilm Corporation | Solid electrolyte composition, mixture, complexed gel, electrode sheet for all-solid state secondary battery, all-solid state secondary battery, and methods for manufacturing solid electrolyte composition, complexed gel, electrode sheet for all-solid state secondary battery and all-solid state secondary battery |
| CN108075181A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of solid-state or colloidal state water-system alkali metal ion battery and preparation method thereof |
| US9960451B1 (en) * | 2017-05-24 | 2018-05-01 | Nanotek Instruments, Inc. | Method of producing deformable quasi-solid electrode material for alkali metal batteries |
| CN107834106A (en) * | 2017-11-13 | 2018-03-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of flexible water system sodium-ion battery |
| CN111196888A (en) * | 2020-01-06 | 2020-05-26 | 浙江大学 | Gel polymer electrolyte doped with modified particles and preparation method and application thereof |
| CN111916850A (en) * | 2020-08-04 | 2020-11-10 | 太仓中科赛诺新能源科技有限公司 | Preparation method and structure of water system quasi-solid sodium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367772A (en) * | 2022-09-15 | 2022-11-22 | 中国石油大学(华东) | Preparation method of prussian blue positive electrode material |
| CN115367772B (en) * | 2022-09-15 | 2023-06-23 | 中国石油大学(华东) | Preparation method of Prussian blue positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113161511B (en) | 2022-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111952579A (en) | High-energy-density sodium ion battery iron-manganese-based positive electrode material and preparation method thereof | |
| CN113161511B (en) | Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof | |
| CN105655152A (en) | Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof | |
| CN109167035A (en) | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation | |
| CN108448168A (en) | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell | |
| CN110176591A (en) | A kind of preparation method of water system zinc ion secondary cell and its anode based on organic electrode materials | |
| CN107565134A (en) | Water system Zinc ion battery based on the tetrone positive pole of pyrene 4,5,9,10 and zinc load | |
| CN103560252A (en) | Flexible lead-acid battery core easy to recycle, and preparation method of flexible lead-acid battery core | |
| CN114373982B (en) | Liquid ether organic electrolyte-based low-negative electrode secondary sodium battery and preparation method thereof | |
| CN104347894A (en) | A sedimentary type aqueous lithium ion battery | |
| CN112234195A (en) | Chargeable and dischargeable water system zinc ion full cell | |
| CN102983368B (en) | Preparation method of high-temperature NI-MH power battery | |
| CN111477872A (en) | Water-based lithium/sodium ion battery with iron-doped sodium titanium phosphate as negative electrode active material and preparation method thereof | |
| CN108075181A (en) | A kind of solid-state or colloidal state water-system alkali metal ion battery and preparation method thereof | |
| CN111146419A (en) | Method for manufacturing long-life lead-acid battery cathode by using trace graphene oxide sheets | |
| CN107681129A (en) | A kind of zinc-base battery three-dimensional zinc/carbon composite and preparation method thereof | |
| CN108598598A (en) | A kind of high-power lithium battery of high specific energy and its manufacturing method | |
| CN103682386A (en) | Battery structure for flow energy storage batteries and all-vanadium flow energy storage battery | |
| CN112018405A (en) | Low-impedance composite bipolar plate brine battery and preparation method thereof | |
| CN107994270B (en) | Horizontal lead-carbon battery and preparation method thereof | |
| CN107452918B (en) | Rare earth new power supply and preparation method thereof | |
| CN107785559B (en) | Graphene-lithium titanate composite material, preparation method thereof, lithium-supplementing graphene-lithium titanate film and lithium battery | |
| CN2786802Y (en) | Vanadium ion liquid current accumulator | |
| CN204596643U (en) | A kind of super capacitance storage battery | |
| CN206225479U (en) | A kind of solid-state or colloidal state water-system alkali metal ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |