CN116053396A - Manufacturing process of sodium ion battery - Google Patents

Manufacturing process of sodium ion battery Download PDF

Info

Publication number
CN116053396A
CN116053396A CN202211654306.XA CN202211654306A CN116053396A CN 116053396 A CN116053396 A CN 116053396A CN 202211654306 A CN202211654306 A CN 202211654306A CN 116053396 A CN116053396 A CN 116053396A
Authority
CN
China
Prior art keywords
current collector
positive electrode
negative electrode
bipolar
material slurry
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
Application number
CN202211654306.XA
Other languages
Chinese (zh)
Other versions
CN116053396B (en
Inventor
陈希雯
常雅慧
朱夏纯
闫坤
车玲娟
孙伟
王俊华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gmcc Electronic Technology Wuxi Co ltd
Original Assignee
Gmcc Electronic Technology Wuxi Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gmcc Electronic Technology Wuxi Co ltd filed Critical Gmcc Electronic Technology Wuxi Co ltd
Priority to CN202211654306.XA priority Critical patent/CN116053396B/en
Publication of CN116053396A publication Critical patent/CN116053396A/en
Application granted granted Critical
Publication of CN116053396B publication Critical patent/CN116053396B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • H01M4/0419—Methods of deposition of the material involving spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • 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

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a rapid preparation process of a sodium ion battery, which comprises the steps of preparing positive electrode material slurry and preparing negative electrode material slurry, respectively adding the positive electrode material slurry and the negative electrode material slurry into high-speed centrifugal equipment, respectively spraying the first positive electrode material slurry and the negative electrode material slurry on the inner side of a positive electrode current collector, the two sides of a bipolar electrode current collector and the inner side of a negative electrode current collector through spray guns after centrifugal acceleration, drying by baking, sequentially laminating, completing metallization of the end part of the bipolar electrode, and sequentially carrying out liquid injection, formation and encapsulation to obtain the battery core of the sodium ion battery. The invention provides a method for preparing a conductive polymer bipolar electrode by continuous centrifugal spraying, which can spray and solidify a micromolecular conductive agent and a binder polymer together by centrifugal mixing, so that the conductive agent can not be segregated and aggregated in the film forming process and can be uniformly dispersed in the binder.

Description

Manufacturing process of sodium ion battery
Technical Field
The invention belongs to the technical field of energy storage devices, and particularly relates to a manufacturing process of a sodium ion battery.
Background
The lithium ion battery has the advantage of high energy density, so that the lithium ion battery is widely applied in modern life, but the current lithium ion battery still cannot meet the requirement of users for longer standby time, so that the development of energy storage device products with higher energy density becomes an urgent requirement in the industry.
With the rapid development of large-scale energy storage technology, lithium ion batteries face the problems of resource shortage, raw material price increase, difficult recovery and the like, and emerging sodium ion batteries increasingly show the advantages. Sodium is abundant in earth crust and widely distributed, and a sodium ion battery and a lithium ion battery have similar deintercalation mechanisms, so that the cycle performance of the lithium ion battery is comparable, and meanwhile, the low-temperature and rate performance of the lithium ion battery is better than that of the lithium ion battery, so that the sodium ion battery becomes a new generation electrochemical system with huge potential.
The battery pack at present basically adopts a grouping mode from a single battery to a module battery pack, ensures the safety of the battery through a multi-level grouping mode, but sacrifices the space utilization rate and the energy density of the battery pack, and a plurality of energy storage units are connected in series through a current collector in the existing battery to form a battery energy storage system, namely a bipolar ETP (Electrode to pack) battery, so that the packaging weight and the volume of the battery can be reduced, the specific energy and the specific power of the battery can be improved, the battery performance and the internal resistance are more stable, the safety of the battery can be greatly improved, but the current commercial bipolar ETP battery has no design of active short-circuit current capacity control, and only has the structural design of passively reinforcing the battery system shell and the like.
The existing bipolar ETP battery adopts a polymer current collector as a matrix of a bipolar electrode, and the polymer has better flexibility and ion conducting performance, can be used as the matrix of the electrode, promotes the performance of the electrode, improves the short-circuit current control capability of the battery and improves the internal resistance, but the traditional centrifugal spraying method is used for preparing the polymer current collector by mixing and stirring materials into slurry and then heating and volatilizing a solvent to form a polymer film. However, this approach is disadvantageous for homogeneous mixing of the multiphase material, which results in a decrease of the mechanical properties of the electrode while the electrochemical properties are difficult to improve significantly.
Disclosure of Invention
In order to solve the problems, the invention provides a manufacturing process of a sodium ion battery.
The technical solution for achieving the above purpose is as follows:
the manufacturing process of the sodium ion battery comprises at least one electric core, wherein the electric core comprises a positive electrode, an electrolyte, a bipolar electrode, a diaphragm and a negative electrode, the positive electrode comprises a positive current collector and a positive active material, the positive active material is arranged on the inner side of the positive current collector, and the positive active material is at least one of transition metal oxide, polyanion compound or Prussian blue compound; the negative electrode comprises a negative electrode current collector and a negative electrode active material, wherein the negative electrode active material is arranged on the inner side of the negative electrode current collector; the bipolar electrode comprises a bipolar electrode current collector, wherein one side of the bipolar electrode current collector is provided with a positive electrode active material, and the other side of the bipolar electrode current collector is provided with a negative electrode active material; the positive electrode and the negative electrode are respectively positioned at the two outermost sides of the battery cell, the bipolar electrode is positioned between the positive electrode and the negative electrode, and the polarities of active material layers arranged on the opposite surfaces of two adjacent electrodes are opposite;
the manufacturing process of the battery comprises the following steps:
s1: selecting a metal foil as a positive electrode current collector, a negative electrode current collector and a bipolar electrode current collector;
s2: mixing an anode active material, a first dispersing agent, a first binder and a first conductive agent to prepare anode material slurry, adding the anode material slurry into high-speed centrifugal equipment, arranging an inflation module, a charging port, a high-speed centrifugal machine, a spray gun and a pulley in the high-speed centrifugal equipment, enabling the anode material slurry to enter the high-speed centrifugal machine through the charging port, enabling the high-speed centrifugal machine to start centrifugal operation, enabling the inflation module to inflate the high-speed centrifugal equipment to enable the high-speed centrifugal machine to have positive pressure, respectively spraying the anode material slurry on the inner side surface of an anode current collector and one surface of a bipolar current collector through the spray gun after the anode material slurry is accelerated through the high-speed centrifugal machine, and controlling the spraying position of the spray gun by the pulley to enable the anode material slurry to be uniformly sprayed on the inner side surface of the anode current collector and one surface of the bipolar current collector;
s3: mixing a negative electrode active material, a second dispersing agent, a second binder and a second conductive agent to prepare a negative electrode material slurry; adding negative electrode material slurry into high-speed centrifugal equipment, enabling the negative electrode material slurry to enter a high-speed centrifugal machine through a charging port, starting centrifugal operation of the high-speed centrifugal machine, enabling an inflation module to inflate the high-speed centrifugal equipment to enable the high-speed centrifugal equipment to have positive pressure, enabling the negative electrode material slurry to be sprayed on the inner side surface of a negative electrode current collector through a spray gun after being accelerated through the high-speed centrifugal machine, and enabling a pulley to control the spraying position of the spray gun to enable the negative electrode slurry to be uniformly sprayed on each current collector;
s4: drying the positive electrode current collector, the bipolar electrode current collector and the negative electrode current collector which are sprayed on both sides, slicing to complete the preparation of each electrode slice, sequentially arranging bipolar electrodes and diaphragms at intervals between the positive electrode and the negative electrode according to the outermost side to complete lamination of the battery cell, carrying out end metallization on the bipolar electrode by adopting a vapor deposition process on the laminated battery cell, and sequentially carrying out injection, formation and encapsulation on the battery cell to obtain the sodium ion battery.
Further improvements, preferably the aeration module in steps S2 and S3 aerates the high speed centrifuge to maintain a pressure within the high speed centrifuge of 2kg/cm 2 -4kg/cm 2 。
Further improvements, it is preferable that the aeration module in steps S2 and S3 aerates the high-speed centrifuge using nitrogen gas so that the gas does not react with the first dispersant and the second dispersant.
Further improved, it is preferable that the rotational speed of the high-speed centrifuge in steps S2 and S3 is maintained at 2000r/min to 4000r/min.
Further improved, the positive electrode current collector in the step S1 is preferably aluminum foil, the negative electrode current collector is copper foil, and the bipolar electrode current collector foil is stainless steel.
In a further improvement, the first dispersing agent in the step S2 is preferably N-methyl pyrrolidone, the first binder is polyvinylidene fluoride, and the first conductive agent is conductive graphite.
In a further improvement, in the step S3, preferably, the negative electrode active material is graphite, the second dispersant is water, the second binder is Styrene Butadiene Rubber (SBR), and the second conductive agent is carbon black S.
In a further improvement, the positive electrode material is preferably a transition metal oxide, the expression of the transition metal oxide is NaxMO2, x is more than 0 and less than or equal to 1, and M is a transition metal element.
Further improvements, it is preferred that the positive electrode material is a polyanionic compound having the expression NaxM 'y [ (POm) n- ] z, M' being a metal ion having a variable valence state.
Further improved, the positive electrode material is preferably Prussian blue compound, the expression of the Prussian blue compound is NaxMA [ MB (CN) 6 ]. ZH2O, and MA and MB are transition metal ions.
The invention is based on the centrifugal spraying technology of the flexible polymer bipolar electrode, and the sodium ion battery with low internal resistance, high controllable safety, low cost, high energy density and power density is obtained, the polymer electrode keeps good electronic conductivity at normal temperature, when the battery system has internal short circuit or needle penetration damage, electrons are accumulated at the damaged part of the short circuit to generate excessive current to generate thermal runaway, the internal resistance of the electrode is influenced by high temperature, the internal current of the electrode is controlled, the heat generated by the short circuit current is reversely reduced, and the electrode with the characteristics can actively inhibit the thermal aggregation risk from the electrode in the initial stage of thermal runaway to be further serious.
The invention provides a method for preparing a conductive polymer electrode by continuous centrifugal spraying. The centrifugal mixing can spray and solidify the micromolecular conductive agent and the binder polymer together, so that the conductive agent can not be segregated and aggregated in the film forming process and is uniformly dispersed in the binder. Experiments prove that compared with a melt calendering method, the conductive polymer prepared by continuous centrifugal spraying has a good film forming effect, maintains the basic mechanical properties of the binder polymer, and also has obviously improved electrochemical properties. In addition, the method can prepare the finished conductive polymer film at one time, can effectively reduce the preparation process, and has considerable application prospect.
Drawings
FIG. 1 is a schematic view of a sodium bipolar battery according to the present invention.
FIG. 2 is a schematic view of a battery with a conductive polymer as a bipolar electrode.
FIG. 3 is a schematic view of a bipolar electrode metal cap structure.
Fig. 4 is a schematic diagram of a high-speed centrifuge apparatus.
FIG. 5 shows a simplified process for preparing the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Referring to fig. 1, a sodium ion battery based on ETP structure includes a plurality of electrode plates assembled into a battery cell in a lamination assembly mode of alternating electrode plates and electrolyte, a housing is covered outside the battery cell, positive electrode active material layers and negative electrode active material layers are respectively arranged on inner side surfaces of two outermost electrode plates, such as an outermost negative electrode piece, an outer positive electrode piece and a battery cell series group, two ends of the battery cell series group are respectively provided with a positive electrode end and a negative electrode end, the outer negative electrode piece is connected with the negative electrode end, the outer positive electrode piece is connected with the positive electrode end, the sodium ion battery includes at least one battery cell 10, the battery cell 10 includes a positive electrode 19, at least one bipolar electrode 18, a diaphragm 13 and a negative electrode 17, the positive electrode 19 includes a positive electrode current collector 16 and a positive electrode active material 15, the positive electrode active material 15 is arranged on the inner side of the positive electrode current collector 16, the negative electrode 17 comprises a negative electrode current collector 11 and a negative electrode active material 12, the negative electrode active material 12 is arranged on the inner side of the negative electrode current collector 11, the bipolar electrode current collector 14 is provided with a positive electrode active material 15 on one side, the negative electrode active material 12 is arranged on the other side, the electrodes are separated by a diaphragm 13, the positive electrode 19 and the negative electrode 7 are respectively positioned on the two outermost sides of the battery core 10, the bipolar electrode 18 is positioned between the positive electrode 19 and the negative electrode 17, the polarities of active material layers arranged on the opposite surfaces of the adjacent two electrodes are opposite, and the bipolar battery is formed by superposing a plurality of battery units in series through the bipolar electrode inside the battery, so that the packaging weight and the volume of the battery can be reduced, the specific energy and the specific power of the battery are improved, and the battery has more stable battery performance and lower internal resistance.
The positive electrode material 15 is at least one of a transition metal oxide having an expression of NaxMO2,0 < x.ltoreq.1, M being a transition metal element, a polyanion compound having an expression of NaxM 'y [ (POm) n- ] z, M' being a metal ion having a variable valence state, a polyanion compound having an expression of NaxMA [ MB (CN) 6 ]. ZH2O, MA and MB being transition metal ions, and the negative electrode materials provided on the surfaces of the bipolar electrode current collector 14 and the negative electrode current collector 11 in this embodiment are graphite, but the present invention is not limited to using only graphite as the negative electrode material.
Meanwhile, in the embodiment, the positive electrode current collector 16 is aluminum foil, the negative electrode current collector 11 is copper foil, and the bipolar current collector 14 is stainless steel foil, but the invention is not limited to the selection of the current collector materials, and all suitable current collector materials are within the protection scope of the application.
The bipolar electrode plates are closely attached to the separator, so that the occupied space of the bipolar electrode plates 14 is reduced, and the volume of the whole battery is reduced. Each bipolar electrode plate comprises an internal current collector, a positive electrode active material layer and a negative electrode active material layer, wherein the positive electrode active material layer and the negative electrode active material layer are respectively coated and arranged on the two side surfaces of the internal current collector, a diaphragm 13 is arranged between each positive electrode active material layer and the adjacent negative electrode active material layer, and the positive electrode active material layer and the negative electrode active material layer are respectively attached to the corresponding internal diaphragm 13, so that the volume of the whole battery cell is further reduced. The bipolar battery is a battery module formed by superposing and connecting a plurality of battery units in series through bipolar electrodes in the battery, and can reduce the packaging weight and the packaging volume of the battery, thereby improving the specific energy and the specific power of the battery, and having more stable battery performance and lower internal resistance.
In contrast, the bipolar battery has the following characteristics that (1) parts such as a tab, a connecting piece, a structural part, a battery shell and the like in the current battery pack do not exist, the ratio of active substances in a battery system is increased, and the specific power and specific energy of the battery system are improved; (2) The current direction is perpendicular to the electrode, the current passes through the very thin bipolar electrode, the current cross-section area is increased while the current transmission path is reduced, the current distribution in the battery is more uniform, the electron transfer channel is shortened, and the internal resistance of the battery is reduced; (3) If a certain battery unit in the bipolar battery is short-circuited, instant heavy current discharge of all battery units in the battery is not caused, only a small amount of heat is generated in the single battery, the battery can be used continuously, and the output voltage of the battery is reduced; (4) The bipolar power batteries are connected in parallel to form a group for use, so that the design of a battery pack management system can be simplified, and the cost of a power battery integrated system can be reduced. In addition, the sodium ion battery has a similar deintercalation mechanism with the lithium ion battery, shows cycle performance comparable to that of the lithium ion battery, and has low temperature and rate capability superior to that of the lithium ion battery.
As shown in fig. 2, in this embodiment, the conductive polymer is coated on the bipolar electrode current collector 14, which has good flexibility and high conductivity, and meanwhile, the polymer is used as the surface film of the bipolar electrode plate, so that the system quality can be further reduced, and the energy density can be improved. As shown in fig. 3, the bipolar electrode plate based on the polymer is metallized by adopting a vapor deposition process, and the metallized bipolar electrode plate is connected with a battery management system by a weldable wire, so that electrochemical monitoring of the electrode plate level in the battery system is realized; in order to facilitate connection of each electrode to the power management system lead-out wires, each polymer current collector, after packaging, will be exposed to a portion at one end of the device, where it is metallized. At present, a polymer film is coated on a bipolar electrode plate generally by adopting a melt casting method, and all component materials are mixed and stirred to form slurry, however, due to large difference of physical properties, the conductive agent is difficult to uniformly disperse in a binder, so that segregation and aggregation of the conductive agent in the polymer can be caused, the mechanical property of the conductive polymer is deteriorated, the performance of a battery is deteriorated, the production speed of the method is low, equipment is expensive, the production process is complex, the heat and capacity consumption is large, and the problems of solvent recovery and safety are considered, so that the prepared polymer film has high cost and low strength.
The invention provides a method for preparing a conductive polymer current collector by continuous centrifugal spraying. The centrifugal mixing can spray and solidify the micromolecular conductive agent and the binder polymer together, so that the conductive agent is not segregated and aggregated in the film forming process, but uniformly dispersed in the binder. Experiments prove that compared with a melt calendering method, the conductive polymer prepared by continuous centrifugal spraying has a good film forming effect, maintains the basic mechanical properties of the binder polymer, and also has obviously improved electrochemical properties. In addition, the method can prepare the finished conductive polymer film at one time, can effectively reduce the preparation process, and has considerable application prospect.
As shown in fig. 4, the high-speed centrifugal device 30 of the present invention includes a feed inlet 21, a spray gun 32, an air charging module 33, a high-speed centrifugal machine 34 and a pulley 35, wherein the air charging module 33 maintains positive pressure in the high-speed centrifugal machine 34, and referring to fig. 5, the specific steps of the preparation process of the sodium ion battery of the present invention are as follows:
s1: the metal foil is selected as the current collectors of the negative electrode 17, the positive electrode 19 and the bipolar electrode 18, the current collector 11 of the negative electrode 17 is selected from copper foil, the current collector 16 of the positive electrode 19 is selected from aluminum foil, the current collector 14 of the bipolar electrode 18 is selected from stainless steel foil, in the embodiment, the bipolar electrode is selected from stainless steel foil, and the surface of the stainless steel foil is easy to form a passivation film, so that the surface of the bipolar electrode can be protected from corrosion, and the bipolar electrode can be simultaneously used as a positive and negative current collector, and the bipolar electrode has the advantages of low cost, simple process, mass production and the like;
s2: the positive electrode material slurry is prepared by mixing a positive electrode active material, a first dispersing agent, a first binder and a first conductive agent, wherein the positive electrode active material in the embodiment adopts at least one of a transition metal oxide, a polyanion compound or a Prussian blue compound, the first dispersing agent adopts N-methyl pyrrolidone, the first binder adopts polyvinylidene fluoride, the first conductive agent adopts conductive graphite, the materials are uniformly mixed to prepare the positive electrode material slurry, the viscosity of the positive electrode slurry in the embodiment is controlled to be 2000-13000 mPa.s, and the viscosity of the positive electrode slurry is more preferably 8000 mPa.s; adding the prepared positive electrode material slurry into a high-speed centrifugal device 30, wherein the high-speed centrifugal device 30 is provided with an inflation module 33, a charging port 31, a high-speed centrifugal device 34, a spray gun 32 and a pulley 35, the positive electrode material slurry enters the high-speed centrifugal device 34 through the charging port 31, the high-speed centrifugal device 34 starts centrifugal operation, the rotating speed of the high-speed centrifugal device 34 is maintained at 2000r/min-4000r/min in the embodiment, the inflation module 33 inflates the high-speed centrifugal device 30 to ensure that the high-speed centrifugal device has positive pressure, and the pressure in the high-speed centrifugal device 34 is maintained at 2kg/cm in the embodiment 2 -4kg/cm 2 The positive electrode material slurry is sprayed on the inner side surface of the positive electrode current collector 16 and one surface of the bipolar electrode current collector 14 through the spray gun 32 after being accelerated by the high-speed centrifugal machine 34, and the pulley 35 controls the spraying position of the spray gun 32, so that the positive electrode slurry is uniformly sprayed on one surface of the positive electrode current collector 16 and one surface of the bipolar electrode current collector 14;
s3: mixing a negative electrode active material, a second dispersing agent, a second binder and a second conductive agent to prepare a negative electrode material slurry, wherein in the embodiment, the negative electrode material is graphite, the second dispersing agent is water, the second binder is Styrene Butadiene Rubber (SBR), the second conductive agent is carbon black, and the materials are uniformly mixed to prepare the negative electrode material slurry, wherein in the embodiment, the viscosity of the negative electrode slurry is controlled to be 2000-13000 mPas, and further preferably, the viscosity of the negative electrode slurry is 6000 mPas; adding the anode material slurry into a high-speed centrifugal device 30, enabling the anode material slurry to enter a high-speed centrifugal machine 34 through a charging port 31, and starting centrifugal operation of the high-speed centrifugal machine 34, wherein the rotating speed of the high-speed centrifugal machine 34 is maintained to be 2000r/min-4 in the embodiment000r/min, the aeration module 33 aerates the high-speed centrifuge apparatus 30 to a positive pressure, and the pressure in the high-speed centrifuge 34 in this embodiment is maintained at 2kg/cm 2 -4kg/cm 2 The anode material slurry is sprayed on the other surface of the bipolar electrode current collector 14 and the inner side surface of the anode current collector 11 through the spray gun 32 after being accelerated by the high-speed centrifugal machine 34, and the pulley 35 controls the spraying position of the spray gun 32, so that the anode material slurry is uniformly sprayed on each current collector;
s4: drying the positive electrode current collector, the bipolar electrode current collector and the negative electrode current collector which are sprayed on both sides, slicing to complete the preparation of each electrode slice, sequentially arranging bipolar electrodes and diaphragms at intervals between the positive electrode and the negative electrode according to the outermost side to complete lamination of the battery cell, carrying out end metallization on the bipolar electrode by adopting a vapor deposition process on the laminated battery cell, and sequentially carrying out injection, formation and encapsulation on the battery cell to obtain the sodium ion battery.
The cathode material slurry/anode material slurry is centrifugally treated, and simultaneously, dispersoids in the cathode material slurry and the anode material slurry and part of the first dispersing agent/second dispersing agent are carried out by gas through inflation pressurization, and are further sprayed out through the nozzle of the spray gun 32, so that solid components in the cathode material slurry/anode material slurry are gathered at the bottom of liquid under the action of centrifugation, and therefore, when the cathode material slurry/anode material slurry is sprayed out by gas, the sprayed components comprise solid components and liquid components, wherein the solid components mainly comprise a first conductive agent insoluble in the first dispersing agent or a second conductive agent insoluble in the second dispersing agent, and the liquid components comprise the first dispersing agent and a first binder dissolved in the first dispersing agent or a second binder dissolved in the second dispersing agent. Due to the centrifugal and carrier gas effects, a plurality of small liquid beads which wrap solid particles are formed at the moment, the solid components in the small liquid beads are wrapped by the liquid components, after the small liquid beads are sprayed on the current collector matrix of the bipolar electrode plate 24, the first dispersing agent/second dispersing agent in the liquid components are removed, the polymer wraps the solid components small particles and are solidified to form a film, the problem of conductive agent segregation in the melt casting coating process can be effectively overcome through the centrifugal spraying process, and the conductive agent is uniformly distributed in the binder polymer, so that the conductive polymer film with a flat and uniform surface can be prepared, the prepared conductive polymer has good mechanical properties, and meanwhile, the electrochemical performance of the battery is also effectively improved due to the fact that the conductive agent is uniformly dispersed and wrapped by the polymer matrix.
The centrifugation speed in the preparation process is not suitable for being too high or too low, and the solid component cannot be fully mixed with the liquid component when too high, so that the adhesive cannot fully wrap the conductive agent; when the rotating speed is too slow, the liquid component cannot be obviously separated from the solid component in the re-centrifugation process, the centrifugation speed is controlled to be 2000-4000 r/min, the high-speed centrifugal machine 34 is inflated by the inflation module 33, but the pressure in the high-speed centrifugal machine 34 is not too high or too low, and the too high pressure can generate huge impact force, so that in the process of spraying the dispersion liquid, the solid component and the liquid component are separated, and a continuous and complete conductive polymer film is difficult to form; too low a pressure makes it difficult to form many dispersed small beads, and eventually the conductive agent still undergoes partial segregation during spraying, and the pressure of the carrier gas is usually 2kg/cm 2 -4kg/cm 2 The optional aeration gas is a gas that does not chemically react with the components of the dispersion, such as nitrogen, oxygen, air.
The flow rate of the slurry affects the thickness of the polymer film, and the effect of the slurry flow rate on the thickness of the coating layer was studied for the positive electrode material slurry and the negative electrode material slurry having a viscosity of 5000mpa·s (25 ℃) and as shown in table 1, it can be seen that the thickness of the coating layer increases with the increase of the flow rate under other conditions.
TABLE 1 flow rate versus coating thickness
Figure 612438DEST_PATH_IMAGE002
The invention researches the effect of 3 kinds of slurries with different viscosities on the coating quality, and the results are shown in Table 2, and the lower the viscosity of the slurry, the better the atomization effect, but the better the atomization effect cannot be explained, the lower the viscosity of the slurry, and the coating possibly generates a flowing phenomenon, wherein the viscosity of the proper slurry is 2000-13000 mPas, the viscosity of the positive electrode material slurry is 8000 mPas, and the viscosity of the negative electrode material slurry is 6000 mPas.
TABLE 2 viscosity of slurries versus coating quality
Figure 857475DEST_PATH_IMAGE004
The invention prepares the ultra-light and safe conductive polymer current collector by a spraying technology, overcomes the defect of direct mixing, improves the mechanical property of the polymer, and prepares the conductive polymer current collector by continuous centrifugal spraying. The centrifugal mixing can spray and solidify the micromolecular conductive agent and the binder polymer together, so that the conductive agent is not segregated and aggregated in the film forming process, but uniformly dispersed in the binder. Experiments prove that compared with a melt calendering method, the conductive polymer prepared by continuous centrifugal spraying has a good film forming effect, maintains the basic mechanical properties of the binder polymer, and also has obviously improved electrochemical properties. In addition, the method can prepare the finished conductive polymer film at one time, can effectively reduce the preparation process, and has considerable application prospect.
The polymer has better flexibility and ion conducting performance, can be used as a substrate of the electrode, and promotes the performance of the electrode. In the conventional centrifugal spraying, materials are mixed and stirred into slurry, and then a volatile solvent is heated to form a composite film, however, the mode is unfavorable for uniform mixing of multiphase materials, and the electrochemical performance of the electrode is difficult to be obviously improved and the mechanical performance of the electrode is reduced. The centrifugal spraying mode provided by the invention is that the ultra-high speed centrifugal machine is utilized to drive the stirring cylinder to rotate at high speed, and the highly atomized paint particles are emitted to the surface of the accessory through the spray head by means of huge centrifugal force, so that a high-quality conductive current collector coating is formed. Compared with airless spraying, the continuous centrifugal spraying has the advantages that: the slurry is highly atomized, atomized particles are uniform, and the linear speed is high; the coating is uniform and smooth, and has no bubbles and pinholes; the coating has good adhesive force and can reach the required thickness by one-time spraying; the construction speed is high and the efficiency is high. The automatic centrifugal spraying mode is adopted to cover the surface of the active material with slurry, namely, the automatic spraying gun is moved up and down to perform uniform spraying operation when the stirring cylinder rotates, so that the defects of uneven thickness, slow exhaust, difficult thickness control and the like of the conductive current collector in the manual spraying mode are avoided. In addition, in the centrifugal spraying process, when the spray gun has the conditions of dripping, blocking and the like, the spray gun can be scraped immediately, the operation is not stopped in the middle, and after the slurry is completely sprayed, the surface of the conductive polymer current collector is checked whether the phenomena of accumulation, skinning, bulge and the like exist. In addition, in the spraying process, the solvent in the slurry can be dispersed along with the spraying process, so that the drying time of the conductive current collector can be greatly shortened. The conductive current collector obtained by the centrifugal spraying mode of the invention has the characteristics of uniform thickness, quick solvent emission, good surface finish, simple and convenient operation and the like. The advantage of the flexible conductive current collector thus prepared by this method is: (1) the thickness uniformity of the conductive current collector is good; (2) more automated than manual spraying; (3) the drying time of the conductive current collector is greatly shortened, and a large amount of energy consumption is saved.
The results of the influence parameters of different methods for preparing the conductive current collector on the film pole piece are shown in table 3, and according to table 3, it can be known that compared with the traditional centrifugal spraying and melt casting methods, the resistivity and the impedance of the conductive polymer prepared by the continuous centrifugal spraying method are obviously reduced, and meanwhile, the conductive polymer can be more uniformly dispersed in the adhesive by adopting the continuous centrifugal spraying method. Further, the active material can undergo more complete reaction thanks to the improvement of the conductivity, and the electrochemical performance of the battery is greatly improved.
TABLE 3 Membrane Pole piece parameters for different preparation methods
Figure DEST_PATH_IMAGE005
The results of the capacity retention rate of the electrode prepared by the continuous centrifugal spraying method of the invention after 50 circles of the electrode are 25 ℃ and 1C, compared with those of the electrode prepared by the traditional centrifugal spraying method are shown in Table 4, and the capacity retention rates of the electrodes obtained by 3 preparation methods are 97.78%, 86.52% and 74.58% respectively after the different electrodes are subjected to 50 circles of the electrode at 25 ℃ and 1C. Among them, the capacity retention of the electrode prepared by the continuous centrifugal spray method is significantly greater than the other two.
Table 4 capacity retention ratio comparison
Figure 748464DEST_PATH_IMAGE006
。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A manufacturing process of a sodium ion battery is characterized in that: the battery comprises at least one cell comprising a positive electrode, an electrolyte, a bipolar electrode, a separator, and a negative electrode;
the positive electrode comprises a positive electrode current collector and a positive electrode active material, wherein the positive electrode active material is arranged on the inner side of the positive electrode current collector, and the positive electrode active material is at least one of transition metal oxide, polyanion compound or Prussian blue compound;
the negative electrode includes a negative electrode current collector and a negative electrode active material disposed inside the negative electrode current collector;
the bipolar electrode comprises a bipolar electrode current collector, wherein one side of the bipolar electrode current collector is provided with a positive electrode active material, and the other side of the bipolar electrode current collector is provided with a negative electrode active material;
the positive electrode and the negative electrode are respectively positioned at the two outermost sides of the battery cell, the bipolar electrode is positioned between the positive electrode and the negative electrode, and the polarities of active material layers arranged on the opposite surfaces of two adjacent electrodes are opposite;
the manufacturing process of the battery comprises the following steps:
s1: selecting a metal foil as a positive electrode current collector, a negative electrode current collector and a bipolar electrode current collector;
s2: mixing an anode active material, a first dispersing agent, a first binder and a first conductive agent to prepare anode material slurry, adding the anode material slurry into high-speed centrifugal equipment, wherein the high-speed centrifugal equipment is provided with an inflation module, a charging port, a high-speed centrifugal machine, a spray gun and a pulley, the anode material slurry enters the high-speed centrifugal machine through the charging port, the high-speed centrifugal machine starts centrifugal operation, the inflation module inflates the high-speed centrifugal equipment to enable the high-speed centrifugal machine to have positive pressure, the anode material slurry is respectively sprayed on the inner side surface of an anode current collector and one surface of a bipolar current collector through the spray gun after being accelerated by the high-speed centrifugal machine, and the pulley controls the spraying position of the spray gun to enable the anode material slurry to be uniformly sprayed on the inner side surface of the anode current collector and one surface of the bipolar current collector;
s3: mixing a negative electrode active material, a second dispersing agent, a second binder and a second conductive agent to prepare a negative electrode material slurry; adding the anode material slurry into high-speed centrifugal equipment, enabling the anode material slurry to enter the high-speed centrifugal machine through the charging port, enabling the high-speed centrifugal machine to start centrifugal operation, enabling the high-speed centrifugal machine to be inflated by the inflation module to enable the high-speed centrifugal machine to have positive pressure, enabling the anode material slurry to be sprayed on the inner side face of the anode current collector through the spray gun after being accelerated by the high-speed centrifugal machine, and enabling the pulley to control the spraying position of the spray gun to enable the anode material slurry to be uniformly sprayed on each current collector;
s4: drying the positive electrode current collector, the bipolar electrode current collector and the negative electrode current collector which are sprayed on both sides, slicing to complete the preparation of each electrode slice, sequentially arranging bipolar electrodes and diaphragms at intervals between the positive electrode and the negative electrode according to the outermost side to complete lamination of the battery cell, carrying out end metallization on the bipolar electrode by adopting a vapor deposition process on the laminated battery cell, and sequentially carrying out injection, formation and encapsulation on the battery cell to obtain the sodium ion battery.
2. The process according to claim 1, wherein the aeration module in steps S2 and S3 aerates the high-speed centrifuge to maintain the pressure in the high-speed centrifuge at 2kg/cm 2 -4kg/cm 2 。
3. The process of claim 2, wherein the aeration module in steps S2 and S3 aerates the high-speed centrifuge with nitrogen gas so that the gas does not react with the first and second dispersants.
4. A process for manufacturing a sodium ion battery according to claim 3, wherein the rotational speed of the high-speed centrifuge in steps S2 and S3 is maintained at 2000r/min to 4000r/min.
5. The process for manufacturing a sodium ion battery according to claim 1, wherein the positive electrode current collector in the step S1 is aluminum foil, the negative electrode current collector is copper foil, and the bipolar electrode current collector foil is stainless steel.
6. The process according to claim 5, wherein the first dispersant in the step S2 is N-methylpyrrolidone, the first binder is polyvinylidene fluoride, and the first conductive agent is conductive graphite.
7. The process according to claim 6, wherein in the step S3, the negative electrode active material is graphite, the second dispersant is water, the second binder is Styrene Butadiene Rubber (SBR), and the second conductive agent is carbon black.
8. The process for manufacturing a sodium ion battery according to claim 1, wherein the positive electrode material is a transition metal oxide, the expression of the transition metal oxide is NaxMO2, x is more than 0 and less than or equal to 1, and M is a transition metal element.
9. The process of claim 1, wherein the positive electrode material is a polyanion compound expressed as NaxM 'y [ (POm) n- ] z, and M' is a metal ion having a variable valence state.
10. The process for manufacturing a sodium ion battery according to claim 1, wherein the positive electrode material is a Prussian blue compound, the Prussian blue compound has a formula of NaxMA [ MB (CN) 6 ]. ZH2O, and MA and MB are transition metal ions.
CN202211654306.XA 2022-12-22 2022-12-22 Manufacturing process of sodium ion battery Active CN116053396B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211654306.XA CN116053396B (en) 2022-12-22 2022-12-22 Manufacturing process of sodium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211654306.XA CN116053396B (en) 2022-12-22 2022-12-22 Manufacturing process of sodium ion battery

Publications (2)

Publication Number Publication Date
CN116053396A true CN116053396A (en) 2023-05-02
CN116053396B CN116053396B (en) 2024-03-22

Family

ID=86120935

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211654306.XA Active CN116053396B (en) 2022-12-22 2022-12-22 Manufacturing process of sodium ion battery

Country Status (1)

Country Link
CN (1) CN116053396B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011009202A (en) * 2009-05-25 2011-01-13 Sumitomo Chemical Co Ltd Method of manufacturing sodium secondary battery, and sodium secondary battery
CN110867578A (en) * 2019-11-21 2020-03-06 江苏理工学院 Sodium ion battery and preparation method and application thereof
CN113272997A (en) * 2019-01-11 2021-08-17 株式会社可乐丽 Nonaqueous electrolyte battery electrode binder, nonaqueous electrolyte battery electrode binder solution, nonaqueous electrolyte battery electrode slurry, nonaqueous electrolyte battery electrode, and nonaqueous electrolyte battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011009202A (en) * 2009-05-25 2011-01-13 Sumitomo Chemical Co Ltd Method of manufacturing sodium secondary battery, and sodium secondary battery
CN113272997A (en) * 2019-01-11 2021-08-17 株式会社可乐丽 Nonaqueous electrolyte battery electrode binder, nonaqueous electrolyte battery electrode binder solution, nonaqueous electrolyte battery electrode slurry, nonaqueous electrolyte battery electrode, and nonaqueous electrolyte battery
CN110867578A (en) * 2019-11-21 2020-03-06 江苏理工学院 Sodium ion battery and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张琰;陶明明;谷巨明;王一菁;: "金属有机框架衍生的Bi/C复合材料作为钠离子电池负极材料的研究", 金属功能材料, no. 01, 15 February 2020 (2020-02-15) *

Also Published As

Publication number Publication date
CN116053396B (en) 2024-03-22

Similar Documents

Publication Publication Date Title
CN108306013B (en) Fast-charging and fast-discharging type high-power lithium ion battery and manufacturing method thereof
US20050285080A1 (en) Electrode composite particles, electrode and electrochemical element, method of manufacturing the electrode composite particles, electrode manufacturing method, electrochemical element manufacturing method
CN111628211A (en) Lithium ion battery and preparation method thereof
CN108232318A (en) A kind of production method of all solid state power lithium-ion battery
CN106410120A (en) Method for supplementing lithium to lithium ion battery pole piece
CN108539252A (en) A kind of high security lithium ion battery
US11855275B2 (en) Method of preparing cathode for secondary battery
CN109980290B (en) Mixed solid-liquid electrolyte lithium storage battery
CN114221045B (en) Preparation method of porous carbon lithium supplementing negative electrode piece lithium ion battery
CN111987375A (en) Boehmite/inert lithium powder composite slurry, lithium-supplementing negative plate, preparation method of negative plate and lithium ion battery
CN105336923A (en) Negative electrode active material, preparation method thereof, and lithium ion battery
CN115714163B (en) Pre-lithium negative plate, preparation method thereof, pre-lithium battery core and lithium ion battery
CN112259724A (en) Composite positive electrode material, preparation method thereof, lithium battery positive electrode material and lithium battery
CN113300051A (en) Method for compounding pole piece and diaphragm of lithium ion battery and lithium ion battery
WO2022253174A1 (en) Current collector and preparation method therefor, negative electrode, and electrochemical energy storage device
CN107507961A (en) A kind of preparation method of conducting polymer modified anode slice of lithium ion battery
CN113131096A (en) Method for compounding pole piece and diaphragm of lithium ion battery and lithium ion battery
CN111786040A (en) Pole piece, application thereof and low-temperature-rise long-life lithium ion battery containing pole piece
CN112615057B (en) Preparation method of solid-state lithium ion battery and solid-state lithium ion battery
CN116053396B (en) Manufacturing process of sodium ion battery
CN115440934A (en) Lithium-containing cathode and preparation method and application thereof
WO2021184534A1 (en) Method of preparing cathode for secondary battery
CN109817467B (en) Composite cathode material and preparation method thereof, and chemical power supply and preparation method thereof
CN113497217A (en) Electrode, preparation method thereof and battery
CN114335550B (en) Preparation method of three-dimensional organic framework composite material, lithium metal cathode and 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