CN114122516A - Incombustible high-safety sodium-ion battery - Google Patents

Incombustible high-safety sodium-ion battery Download PDF

Info

Publication number
CN114122516A
CN114122516A CN202111303810.0A CN202111303810A CN114122516A CN 114122516 A CN114122516 A CN 114122516A CN 202111303810 A CN202111303810 A CN 202111303810A CN 114122516 A CN114122516 A CN 114122516A
Authority
CN
China
Prior art keywords
sodium
electrolyte
ion battery
carbon
phosphate
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.)
Pending
Application number
CN202111303810.0A
Other languages
Chinese (zh)
Inventor
王永刚
周康
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.)
Fudan University
Original Assignee
Fudan University
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 Fudan University filed Critical Fudan University
Priority to CN202111303810.0A priority Critical patent/CN114122516A/en
Publication of CN114122516A publication Critical patent/CN114122516A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62C—FIRE-FIGHTING
    • A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
    • A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Public Health (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of electrochemistry, and particularly relates to a non-combustible high-safety sodium ion battery. The electrolyte comprises a sodium salt, an ester solvent and a flame retardant; wherein the sodium salt is selected from NaNO3、Na2SO4、Na3PO4、NaI、NaPF6One or more of NaTFSI, NaFSI or NaTFMS, wherein the flame retardant is selected from one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, diphenyl isopropylbenzene phosphate or hexamethyl phosphoramideOr several of them. The electrolyte used by the traditional sodium ion battery is combustible, which is harmful to the safety of the battery. The sodium ion battery electrolyte provided by the invention is non-combustible, so that the sodium ion battery electrolyte has safer characteristics compared with the traditional sodium ion battery, and has a certain application prospect in the aspects of large-scale energy storage and power batteries.

Description

Incombustible high-safety sodium-ion battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a non-combustible high-safety sodium ion battery.
Background
In recent years, sodium ion batteries have been rapidly developed and widely used in various industries. Sodium ion batteries have become an indispensable part, especially in new energy storage and mobile electronic devices. However, as the use of sodium ion batteries has become widespread, higher and higher requirements have been put on sodium ion batteries. How to improve the safety of the sodium ion battery becomes an unavoidable problem. The electrolyte is an important part of sodium ion batteries, and is a focus of attention for the first time.
Currently, organic solvents such as EC (ethylene carbonate), DMC (ethyl methyl carbonate), and DEC (diethyl carbonate) are commonly used as electrolyte solvents in sodium ion batteries. The organic solvents have the characteristic of flammability, which brings hidden trouble for safe use of the sodium-ion battery. And due to the solubility problem of the organic solvents, some cheap inorganic sodium salts (such as sodium nitrate or sodium sulfate) cannot be dissolved in the ester electrolytes, further hindering the practical application of the ester electrolytes, and being not beneficial to the mass production and sustainable development of sodium ion batteries.
Although many researchers have conducted research on these problems, the problems of flammability and inorganic salt solubility still cannot be solved well.
Disclosure of Invention
The invention aims to provide a non-flammable high-safety sodium ion battery. The sodium ion battery provided by the invention has excellent electrochemical performance, and meanwhile, the electrolyte is non-combustible, so that the sodium ion battery has the characteristics of safety, low price and the like compared with the traditional sodium ion battery, and has a certain application prospect in the aspects of large-scale energy storage and power batteries. The technical scheme of the invention is specifically introduced as follows.
A non-combustible sodium ion battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte comprises a sodium salt, an ester solvent and a flame retardant; wherein the sodium salt is selected from NaNO3、Na2SO4、Na3PO4、NaI、NaPF6One or more of NaTFSI (sodium bis (trifluoromethylsulfonyl) imide), NaFSI (sodium bis fluorosulfonylimide) or NaTFMS (sodium trifluoromethanesulfonate), wherein the flame retardant is one or more selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, diphenyl isopropylphosphate or hexamethyl phosphoramide.
Preferably, the ester solvent is one or more selected from fluoroethylene carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl propionate, methyl butyrate, butyl acetate, methyl propionate and propyl butyrate.
Preferably, the volume ratio of the ester solvent to the flame retardant is 2: 1-8: 1.
Preferably, the concentration of the sodium salt in the electrolyte is 0.5-5 mol/L.
Preferably, the electrolyte further comprises a polymer framework material for enabling the electrolyte to form a gel quasi-solid electrolyte.
Preferably, the polymer skeleton material is selected from one or more of polyethylene oxide PEO, polybutyl acrylate PBA, polyacrylonitrile PAN, polymethyl methacrylate PMMA or polypropylene oxide PPO.
Preferably, the sodium salt in the electrolyte is NaNO3Or Na2SO4The electrolyte comprises an electrolyte, an ester solvent and a flame retardant, wherein the ester solvent in the electrolyte is one or more of fluoroethylene carbonate, methyl ethyl carbonate, diethyl carbonate or dimethyl carbonate, the flame retardant in the electrolyte is one or two of trimethyl phosphate or triethyl phosphate, the volume ratio of the ester solvent to the flame retardant is 3: 1-4: 1, and the electrolyte also comprises polybutyl acrylate PBA.
Preferably, the positive electrode is composed of a positive electrode active material, a conductive agent, a binder and a current collector, and the negative electrode is metal sodium or is composed of a negative electrode active material, a conductive agent, a binder and a current collector; wherein: the positive active material is selected from NaCrO with a laminated structure2、NaNiO2、NaCoO2、Na0.44MnO2、NaNixCoyMzO2(M-Al or Mn; x + y + z-1), Na in phosphate structure3V2(PO4)3、Na7V4(P2O7)4(PO)、NaFePO4、Na4Fe3(PO4)2P2O7、Na2FeP2O7NaNiFe (CN) of Prussian blue Structure6、Na2MnMn(CN)6Any one of (a); the negative active material is selected from hard carbon and soft carbonAny of sodium tin complexes or sulfides.
Preferably, the positive electrode active material is Na3V2(PO4)3、Na4Fe3(PO4)2P2O7、Na2FeP2O7、NaNiFe(CN)6The negative electrode active material is selected from any one of hard carbon and soft carbon.
Preferably, when the positive electrode and the negative electrode are prepared, the adopted binder is independently one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), water-soluble rubber, polyvinyl alcohol (PVA), polyacrylic acid (PAA), Sodium Alginate (SA) or acrylonitrile multipolymer LA132/LA133, the conductive agent is independently one of acetylene black, carbon nano tubes, carbon fibers, graphene, graphite or mesoporous carbon, and the current collector is independently one of an aluminum net, an aluminum foil, a carbon-coated aluminum foil, a titanium net, a titanium foil, a stainless steel net, a stainless steel foil, a porous stainless steel belt, carbon cloth, a carbon felt, a carbon net, a copper net or a copper foil.
Preferably, the binder is one of polyvinylidene fluoride (PVDF) and carboxymethylcellulose (CMC), the conductive agent is one of acetylene black and carbon black, and the current collectors of the positive electrode and the negative electrode are one of carbon-coated aluminum foil and copper foil.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing a nonflammable sodium-ion battery electrolyte, which is characterized in that a flame retardant additive capable of dissolving conventional inorganic sodium salt (such as sodium nitrate or sodium sulfate) is added into a common sodium-ion battery electrolyte, and the inorganic sodium salt or fluorine-containing sodium salt is selectively added as an electrolyte according to actual needs to prepare the nonflammable sodium-ion battery electrolyte. The high-safety electrolyte is more beneficial to the application of the sodium ion battery to industries such as electric automobiles and the like, and can effectively reduce the manufacturing cost when inorganic sodium salt is used, so that the sodium ion battery can be produced and applied in a large scale.
In the invention, inorganic sodium salt (such as sodium nitrate or sodium sulfate), ester solvent and flame retardant are used as electrolyte, an intercalation compound is used as a positive electrode, one of hard carbon, soft carbon, sodium-tin compound and the like is used as a negative electrode to form a full battery, and the sodium-ion battery which is nonflammable, low in cost and stable in circulation can be obtained. The battery has the characteristics of high safety and low cost, and is favorable for popularization and large-scale production.
Detailed Description
To further clearly illustrate the technical solutions and advantages of the present invention, the present invention is described by the following specific examples, but the present invention is not limited to these examples.
Example 1
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium nitrate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na3V2(PO4)3As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)3V2(PO4)3): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, a 2032 button cell was assembled with sodium metal (Na) as the negative electrode material and Celgard 2500 membrane as the separator. Under the current density of 1C at the normal temperature of 25 ℃, the capacity of the first circle is 115mAh/g, after 475 circles are circulated, the capacity retention rate reaches 93%, and the average coulombic efficiency is 99.7%. (see Table 1)
Example 2
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) are mixed according to the volume ratio of 1:1:2, then 30% of butyl acrylate monomer by volume ratio is added into the uniform solution, and then sodium nitrate is added to prepare 1mol/L solution. Azobisisobutyronitrile (AIBN) was then dissolved in the solution as a thermal initiator. The resulting solution was injected into a glass mold with silicone spacers. Finally, the electrolyte is heated for 12 hours at 70 ℃ to obtain the quasi-solid local high-concentration electrolyte. The prepared quasi-solid electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na3V2(PO4)3As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)3V2(PO4)3): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, a 2032 button cell was assembled with sodium metal (Na) as the negative electrode material and Celgard 2500 membrane as the separator. At the normal temperature of 25 ℃, the capacity of the first circle is 113mAh/g at the current density of 1C, after 650 circles of circulation, the capacity retention rate reaches 91%, and the average coulombic efficiency is 99.5%. (see Table 1).
Example 3
Diethyl carbonate (DEC) and triethyl phosphate (TEP) were mixed in a volume ratio of 3:1, and sodium sulfate was added as a solute to prepare an electrolyte solution having a concentration of 1 mol/L. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na3V2(PO4)3As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)3V2(PO4)3): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, hard carbon is used as a negative electrode active material. Mixing hard carbon: conductive agent (super P): the slurry was mixed with a binder (sodium carboxymethylcellulose CMC) at a ratio of 80:10:10, and coated on the surface of a copper foil to form a negative electrode sheet. A 2032 button cell was assembled using Celgard 2500 membrane as separator. Under the normal temperature of 25 ℃, the capacity of the first circle is 116mAh/g at the current density of 1C, after 850 circles of circulation, the capacity retention rate reaches 90.6%, and the average coulombic efficiency reaches 99.4%. (see Table 1).
Example 4
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium sulfate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na3V2(PO4)3As positive electrodeAnd (4) a sexual substance. The preparation of the positive electrode plate is as follows: according to the active substance (Na)3V2(PO4)3): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, soft carbon is used as a negative electrode active material. Mixing the soft carbon: conductive agent (super P): the slurry was mixed with a binder (sodium carboxymethylcellulose CMC) at a ratio of 80:10:10, and coated on the surface of a copper foil to form a negative electrode sheet. A 2032 button cell was assembled using Celgard 2500 membrane as separator. At the normal temperature of 25 ℃, under the current density of 1C, the capacity of the first circle is 108mAh/g, after the circulation is carried out for 400 circles under the current density of 2C, the capacity retention rate reaches 93.8 percent, and the average coulombic efficiency reaches 99.2 percent. (see Table 1).
Example 5
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium nitrate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With NaNiFe (CN)6As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (NaNiFe (CN))6): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, a 2032 button cell was assembled with sodium metal (Na) as the negative active material and Celgard 2500 membrane as the separator. At the normal temperature of 25 ℃, under the current density of 1C, the capacity of the first circle is 70mAh/g, after 300 circles of circulation, the capacity retention rate reaches 95%, and the average coulombic efficiency is 99.7%. (see Table 1).
Example 6
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium nitrate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With NaNiFe (CN)6As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (NaNiFe (CN))6): conductive agent (super P): bonding ofThe slurry is mixed according to the proportion of 80:10:10 of polyvinylidene fluoride (PVDF), and the mixture is coated on the surface of the carbon-coated aluminum foil to form the positive electrode slice. Next, hard carbon is used as a negative electrode active material. Mixing hard carbon: conductive agent (super P): the slurry is mixed with a binder (sodium carboxymethylcellulose (CMC): 80:10: 10) and coated on the surface of copper foil to form a negative electrode sheet, and a 2032 button cell is assembled by using a Celgard 2500 film as a diaphragm. Under the normal temperature of 25 ℃, the capacity of the first circle is 68mAh/g at the current density of 1C, after 500 circles of circulation, the capacity retention rate reaches 92%, and the average coulombic efficiency is 99.2%. (see Table 1).
Example 7
Dimethyl carbonate (DMC) and triethyl phosphate (TEP) were mixed in a volume ratio of 3:1, and then sodium nitrate was added as a solute to prepare an electrolyte solution having a concentration of 1 mol/L. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na2FeP2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FeP2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, soft carbon is used as a negative electrode active material. Mixing the soft carbon: conductive agent (super P): the slurry was mixed with a binder (sodium carboxymethylcellulose CMC) at a ratio of 80:10:10, and coated on the surface of a copper foil to form a negative electrode sheet. A 2032 button cell was assembled using Celgard 2500 membrane as separator. At the normal temperature of 25 ℃, the capacity of the first circle is 66mAh/g at the current density of 1C, and after 900 circles are circulated at the current density of 2C, the capacity retention rate reaches 91%, and the average coulombic efficiency reaches 99.1%. (see Table 1).
Example 8
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium nitrate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na2FeP2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)2FeP2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, hard carbon is used as a negative electrode active material. Mixing hard carbon: conductive agent (super P): the slurry was mixed with a binder (sodium carboxymethylcellulose CMC) at a ratio of 80:10:10, and coated on the surface of a copper foil to form a negative electrode sheet. A 2032 button cell was assembled using Celgard 2500 membrane as separator. Under the current density of 1C at the normal temperature of 25 ℃, the capacity of the first circle is 65mAh/g, after 500 circles of circulation, the capacity retention rate reaches 91.3%, and the average coulombic efficiency reaches 99.5%. (see Table 1).
Example 9
Dimethyl carbonate (DMC) and triethyl phosphate (TEP) were mixed in a volume ratio of 3:1, and sodium sulfate was added as a solute to prepare an electrolyte solution having a concentration of 1 mol/L. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na4Fe3(PO4)2P2O7As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active substance (Na)4Fe3(PO4)2P2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Metallic sodium (Na) was used as a negative electrode active material. A 2032 button cell was assembled using Celgard 2500 membrane as separator. At the normal temperature of 25 ℃, the capacity of the first circle is 98mAh/g at the current density of 1C, after 300 circles of circulation, the capacity retention rate reaches 95%, and the average coulombic efficiency reaches 99.3%.
(see Table 1).
Example 10
Trimethyl phosphate (TMP), fluoroethylene carbonate (FEC) and Ethyl Methyl Carbonate (EMC) were mixed in a volume ratio of 1:1:2, and then sodium nitrate was added to prepare a 1mol/L solution. The prepared electrolyte is placed on the flame of an alcohol lamp for 10 seconds, and the electrolyte is not ignited. With Na4Fe3(PO4)2P2O7As a positive electrode active material. Positive electrodeThe preparation of the pole piece is as follows: according to the active substance (Na)4Fe3(PO4)2P2O7): conductive agent (super P): and (3) mixing the slurry with a binder (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10, and coating the slurry on the surface of the carbon-coated aluminum foil to form the positive electrode sheet. Next, metal sodium (Na) was used as a negative electrode active material. A 2032 button cell was assembled using Celgard 2500 membrane as separator. Under the normal temperature of 25 ℃, the capacity of the first circle is 96mAh/g at the current density of 1C, after 700 circles of circulation, the capacity retention rate reaches 90.1%, and the average coulombic efficiency reaches 99.5%. (see Table 1).
Table 1 comparison of cycle performance of sodium ion batteries using different electrode materials and electrolytes
Figure BDA0003339372430000061
Figure BDA0003339372430000071

Claims (10)

1. A non-flammable high-safety sodium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the electrolyte comprises sodium salt, an ester solvent and a flame retardant; wherein the sodium salt is selected from NaNO3、Na2SO4、Na3PO4、NaI、NaPF6The flame retardant is one or more selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, diphenyl isopropyl phosphate or hexamethyl phosphoramide.
2. The high-safety sodium-ion battery according to claim 1, wherein the ester solvent is one or more selected from fluoroethylene carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl propionate, methyl butyrate, butyl acetate, methyl propionate, and propyl butyrate.
3. The high-safety sodium-ion battery according to claim 1, wherein the volume ratio of the ester solvent to the flame retardant is 2:1 to 8: 1.
4. The high safety sodium ion battery of claim 1, further comprising a polymer backbone material in the electrolyte for the electrolyte to form a gel quasi-solid electrolyte.
5. The high-safety sodium-ion battery according to claim 4, wherein the polymer skeleton material is selected from one or more of polyethylene oxide (PEO), polybutyl acrylate (PBA), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) or polypropylene oxide (PPO).
6. The sodium ion battery of claim 1, wherein the sodium salt in the electrolyte is NaNO3Or Na2SO4The electrolyte comprises an electrolyte, an ester solvent and a flame retardant, wherein the ester solvent in the electrolyte is one or more of fluoroethylene carbonate, methyl ethyl carbonate, diethyl carbonate or dimethyl carbonate, the flame retardant in the electrolyte is one or two of trimethyl phosphate or triethyl phosphate, the volume ratio of the ester solvent to the flame retardant is 3: 1-4: 1, and the electrolyte also comprises polybutyl acrylate PBA.
7. The high-safety sodium-ion battery according to claim 1, wherein the positive electrode is prepared by preparing mixed slurry from a positive active material, a conductive agent and a binder and then coating the mixed slurry on the surface of a current collector, and the negative electrode is prepared by preparing mixed slurry from a negative active material, a conductive agent and a binder and then coating the mixed slurry on the surface of the current collector; wherein: the positive active material is selected from NaCrO with a laminated structure2、NaNiO2、NaCoO2、Na0.44MnO2、NaNixCoyMzO2M = Al or Mn, x + y + z =1, Na of phosphate structure3V2(PO4)3、Na7V4(P2O7)4(PO)、NaFePO4、Na4Fe3(PO4)2P2O7、Na2FeP2O7NaNiFe (CN) of Prussian blue Structure6、Na2MnMn(CN)6Any one of (a); the negative electrode active material is selected from any one of hard carbon, soft carbon, sodium-tin complex, or sulfide.
8. The sodium ion battery of claim 7, wherein the positive electrode active material is Na3V2(PO4)3、Na4Fe3(PO4)2P2O7、Na2FeP2O7、NaNiFe(CN)6The negative electrode active material is selected from any one of hard carbon and soft carbon.
9. The high-safety sodium-ion battery according to claim 7, wherein when the positive electrode and the negative electrode are prepared, the binder is one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), water-soluble rubber, polyvinyl alcohol (PVA), polyacrylic acid (PAA), Sodium Alginate (SA) or acrylonitrile multipolymer LA132/LA133, the conductive agent is one of acetylene black, carbon nanotube, carbon fiber, graphene, graphite or mesoporous carbon, and the current collector is one of aluminum mesh, aluminum foil, carbon-coated aluminum foil, titanium mesh, titanium foil, stainless steel mesh, stainless steel foil, porous stainless steel band, carbon cloth, carbon felt, carbon mesh, copper mesh or copper foil.
10. The high-safety sodium-ion battery according to claim 9, wherein the binder is independently any one of polyvinylidene fluoride (PVDF) and carboxymethylcellulose (CMC), the conductive agent is independently any one of acetylene black or carbon black, and the current collectors of the positive electrode and the negative electrode are independently one of carbon-coated aluminum foil or copper foil.
CN202111303810.0A 2021-11-05 2021-11-05 Incombustible high-safety sodium-ion battery Pending CN114122516A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111303810.0A CN114122516A (en) 2021-11-05 2021-11-05 Incombustible high-safety sodium-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111303810.0A CN114122516A (en) 2021-11-05 2021-11-05 Incombustible high-safety sodium-ion battery

Publications (1)

Publication Number Publication Date
CN114122516A true CN114122516A (en) 2022-03-01

Family

ID=80380703

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111303810.0A Pending CN114122516A (en) 2021-11-05 2021-11-05 Incombustible high-safety sodium-ion battery

Country Status (1)

Country Link
CN (1) CN114122516A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114792843A (en) * 2022-03-02 2022-07-26 温州大学碳中和技术创新研究院 Sodium ion battery high-voltage electrolyte suitable for high-voltage positive electrode material, and preparation method and application thereof
CN116826162A (en) * 2023-08-28 2023-09-29 河南新太行电源股份有限公司 Solid sodium ion battery and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105655631A (en) * 2016-03-30 2016-06-08 武汉大学 Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery
CN106030888A (en) * 2014-02-21 2016-10-12 住友化学株式会社 Sodium secondary battery
CN108172816A (en) * 2017-12-26 2018-06-15 深圳先进技术研究院 Sodium base Dual-ion cell and preparation method thereof
CN108899582A (en) * 2018-07-10 2018-11-27 中国科学院长春应用化学研究所 A kind of flame retardant type electrolyte and Dual-ion cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106030888A (en) * 2014-02-21 2016-10-12 住友化学株式会社 Sodium secondary battery
CN105655631A (en) * 2016-03-30 2016-06-08 武汉大学 Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery
CN108172816A (en) * 2017-12-26 2018-06-15 深圳先进技术研究院 Sodium base Dual-ion cell and preparation method thereof
CN108899582A (en) * 2018-07-10 2018-11-27 中国科学院长春应用化学研究所 A kind of flame retardant type electrolyte and Dual-ion cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114792843A (en) * 2022-03-02 2022-07-26 温州大学碳中和技术创新研究院 Sodium ion battery high-voltage electrolyte suitable for high-voltage positive electrode material, and preparation method and application thereof
CN116826162A (en) * 2023-08-28 2023-09-29 河南新太行电源股份有限公司 Solid sodium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN109962222B (en) Method for preparing lithium-sulfur battery positive electrode material by using bacterial cellulose hydrogel
CN109103399B (en) Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery
CN105811007A (en) Electrolyte gel, lithium-sulfur battery and method for preparing electrolyte gel
CN108807808B (en) Preparation method of biomass carbon aerogel modified lithium-sulfur battery diaphragm
CN114122516A (en) Incombustible high-safety sodium-ion battery
CN103367791B (en) A kind of new type lithium ion battery
CN110190284B (en) Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof
CN111952670A (en) Lithium ion battery with wide working temperature range
CN113937336A (en) Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode
CN113651935A (en) Porous polymer-sulfur composite material and preparation method and application thereof
CN113851710A (en) Sodium ion bifunctional gel polymer electrolyte, and preparation method and application thereof
CN113422053A (en) Battery negative electrode material based on tricyclic quinazoline and derivative thereof and application of battery negative electrode material in alkali metal ion battery
CN111477854B (en) Composite nano material and preparation method and application thereof
CN105161689A (en) Preparing method and application of polypyrrole/multi-wall carbon nanotube/sulfur composite material
CN110556537B (en) Method for improving electrochemical performance of anion-embedded electrode material
CN110854357A (en) Preparation method of nano carbon fiber negative electrode material electrode plate embedded with silicon particles
CN107946582B (en) Lithium-sulfur battery positive electrode material, preparation method thereof, lithium battery positive electrode and lithium battery
CN116470129A (en) Hydroxyapatite fiber composite solid electrolyte and preparation method and application thereof
CN103834153A (en) Gel polymer electrolyte and preparation method thereof
CN116435592A (en) High-voltage ether gel electrolyte and preparation method and application thereof
CN115295865A (en) Preparation method of in-situ polymerization solid polymer electrolyte lithium ion battery
CN114122497A (en) Lithium ion battery with high safety, low price and environmental protection
CN110323079A (en) A kind of high pressure resistant anion exchange dielectric film and its solid state battery capacitor
CN116666585B (en) Negative electrode material of sodium ion battery, negative electrode plate and sodium ion battery
CN115602924A (en) Flame-retardant sodium-ion battery electrolyte and application thereof

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