CN108735976A - A kind of preparation method of electrostatic spinning lithium ion battery negative electrode - Google Patents

A kind of preparation method of electrostatic spinning lithium ion battery negative electrode Download PDF

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Publication number
CN108735976A
CN108735976A CN201810318710.7A CN201810318710A CN108735976A CN 108735976 A CN108735976 A CN 108735976A CN 201810318710 A CN201810318710 A CN 201810318710A CN 108735976 A CN108735976 A CN 108735976A
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China
Prior art keywords
spinning
electrostatic spinning
copper foil
lithium ion
preparation
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CN201810318710.7A
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Chinese (zh)
Inventor
廖小东
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Dongfang Electric Corp
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Dongfang Electric Corp
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Priority to CN201810318710.7A priority Critical patent/CN108735976A/en
Publication of CN108735976A publication Critical patent/CN108735976A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1397Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • 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)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses a kind of preparation method of electrostatic spinning lithium ion battery negative electrode, includes the following steps:Polyoxometallic acid lithium salts is dissolved in deionized water, polyoxometallic acid lithium salt solution is formed;Graphite is added in polyoxometallic acid lithium salt solution, and surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added, aqueous adhesive LA13x forms spinning solution;Spinning solution is fitted into electrostatic spinning machine and carries out spinning, spinning solution is spun on copper foil, strand it is fine and close and it is uniform be bonded on copper foil, then will be bonded with the copper foil drying of strand, the negative pole piece of battery is made.Cathode pole piece is prepared using electrostatic spinning process and stirs coating process compared to tradition, the process time is shortened, improves production efficiency.

Description

A kind of preparation method of electrostatic spinning lithium ion battery negative electrode
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of electrostatic spinning lithium ion battery negative electrodes Preparation method.
Background technology
Representative of the lithium ion battery as green energy resource, is obtaining great development in recent years, and it is dynamic to be gradually applied to automobile Power battery and energy-storage battery field.But due to the defect of lithium ion battery material and technique, its power and energy storage field are limited Large-scale application, be only capable of at present be in demonstration phase, traction is not high, main reason is that battery itself polarization and it is interior The influence of resistance.The influence factor of polarization and internal resistance has electronic conductivity and lithium-ion-conducting, at present lithium battery material very great Cheng Electronic conductivity can be met on degree, but lithium-ion-conducting is to be improved.And traditional lithium ion battery preparation process includes stirring It mixes, is coated with, the processes such as roll-in, process is complicated, and the consuming time is long, low production efficiency.
It is 201610698802.3 separately to have Chinese Patent Application No., and a kind of lithium ion battery is disclosed in 2016.12.14, Using nickel tungstate nanofiber as negative material.The invention also discloses the preparation methods of lithium ion battery negative material:First 20mL deionized waters are measured, then 0 .5912g of ammonium metatungstate hydrate, four water acetic acid nickel 0.5972g are add to deionized water, It is stirred well to and is completely dissolved, 1.2g polyvinylpyrrolidones are then added, stir to being completely dissolved, obtain electrostatic spinning forerunner Liquid solution, then electrostatic spinning precursor solution is fitted into 10mL syringes, then syringe is put into electrostatic spinning machine, it will Solution promotes rate to be set as 0.6mL/h, and voltage is set as 12KV, and nozzle is set as 12cm with spinning receiver board distance, is collected with aluminium foil Spinning, after spinning is removed from aluminium foil, annealing is raised to 670 DEG C, 1h is kept the temperature under conditions of 670 DEG C, to be made For the nickel tungstate nanofiber of lithium ion battery negative material.Although foregoing invention is prepared only using electrostatic spinning, the party It is negative material, also needs to carry out slurry preparation, thus production efficiency according to tradition stirring coating method after obtaining negative material It is relatively low.
Invention content
In order to overcome the deficiencies of existing technologies, the present invention provides a kind of systems of electrostatic spinning lithium ion battery negative electrode Preparation Method, negative material prepared by this method reduce the internal resistance of cell and polarization, shorten the process time, improve production effect Rate.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is:
A kind of preparation method of electrostatic spinning lithium ion battery negative electrode, which is characterized in that include the following steps:
(1) polyoxometallic acid lithium salts is dissolved in deionized water, forms polyoxometallic acid lithium salt solution;
(2) graphite is added in polyoxometallic acid lithium salt solution, and surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added, it is aqueous viscous Agent LA13x is met, spinning solution is formed;
(3) spinning solution is fitted into electrostatic spinning machine and carries out spinning, receiver board is copper foil, spinning head be it is multigroup, spinning head with The distance of receiver board is 0.1-8cm;Voltage is 16-20KV;Jet speed is 0.1-0.3mL/S, and strand is fine and close and uniform to be glued It is connected on copper foil, then the copper foil for being bonded with strand is dried, the negative pole piece of battery is made.
In the step (3), copper foil is driven using coating machine, the transmission speed of coating machine and the jet quick of electrostatic spinning machine Degree is adjusted and is adapted, and the strand being bonded on copper foil that is adapted is non-overlapping, fine and close and uniform.
In the step (3), spinning head is 5cm at a distance from receiver board;Voltage is 18KV;Jet speed is 0.2mL/S.
The polyoxometallic acid lithium salts is Li3XY12O40, Li4XY12O40One or more of mixture, wherein:X Refer to any one in two kinds of elements of P, Si;Y refers to any one in two kinds of elements of Mo, W.
The spinning diaphragm of drying is cut into cathode pole piece.Anode uses conventional cathode blank preparation technics with LiFePO4 It is prepared into anode slice of lithium ion battery, and is assembled into battery testing.
The present invention has the following advantages:
1. the present invention to electrostatic spinning by preparing graphite cathode pole of the lithium ion battery negative electrode compared to traditional lithium battery Piece has following advantage:Influencing the internal resistance of cell and polarization has electronic conduction and lithium ion conduction, traditional graphite cathode pole piece Though can meet the requirement of electronic conduction, due to the interlayer structure of graphite, lithium ion conduction is unsatisfactory, the internal resistance of cell and It polarizes larger;And polyoxometallic acid lithium salts and the compound material of graphite are used, and because of the three-dimensional framework of polyoxometallic acid lithium salts, lithium Ion can transmit wherein, greatly improve the transmission rate of lithium ion, the synergistic effect of the two, make electronics and lithium ion Conduction has larger promotion compared to conventional graphite, reduces the internal resistance of cell and polarization, is conducive to improve battery performance.
2. the present invention prepares cathode pole piece using electrostatic spinning process and stirs coating process compared to tradition, work is shortened The skill time, improve production efficiency.
3. spinning head of the present invention is multigroup, to improve production efficiency, device for spinning quantity can be configured according to actual conditions.
4. the polyoxometallic acid lithium salts Li of the present invention3XY12O40, Li4XY12O40One or more of mixture(X Refer to any one in two kinds of elements of P, Si;Y refers to any one in two kinds of elements of Mo, W)Reduction-state.Select a few more metals of class Oxygen hydrochlorate series structure is most stable, resource foot, and production cost is low.
Specific implementation mode
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment, the sides Method is conventional method unless otherwise instructed, and the material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1
A kind of preparation method of electrostatic spinning lithium ion battery negative electrode, includes the following steps:
(1) by polyoxometallic acid lithium salts Li3PMo12O40It is dissolved in deionized water, forms polyoxometallic acid lithium salt solution;
(2) graphite is added in polyoxometallic acid lithium salt solution, and surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added, it is formed Spinning solution;Aqueous adhesive LA13x is:Acrylonitrile multiple copolymer, respectively LA132, LA133 and LA135's is any.
(3) spinning solution is fitted into electrostatic spinning machine and carries out spinning, receiver board is copper foil, and spinning head is multigroup, spinneret Head is 0.1-8cm at a distance from receiver board(Optimum distance is 5cm);Voltage is 16-20KV(Most preferably 18Kv);Jet speed is 0.1-0.3mL/S(Optimum flow rate 0.2mL/S), strand it is fine and close and it is uniform be bonded on copper foil, then will be bonded with strand Copper foil is dried, and the negative pole piece of battery is made.Electrostatic spinning machine is used cooperatively with coating machine, and the moving direction of copper foil is coating The transmission speed of the transmission direction of machine, coating machine is adjusted according to the jet speed of device for spinning, spinning solution is spun on copper foil, together When ensure that the spinneret strand on copper foil is fine and close and uniform;The baking oven that coating machine is accessed in transmission direction, by the spinning film copper of formation Piece is dried.
The spinning film copper sheet of drying is cut into cathode pole piece.
Anode is prepared into anode slice of lithium ion battery with LiFePO4 using conventional cathode blank preparation technics, and assembles At battery testing.
Embodiment 2
Preparation method and test method only change polyoxometallic acid lithium salts into Li with embodiment 13PW12O40
Embodiment 3
Preparation method and test method only change polyoxometallic acid lithium salts into Li with embodiment 14SiMo12O40
Embodiment 4
Preparation method and test method only change polyoxometallic acid lithium salts into Li with embodiment 14SiW12O40
Comparative example 1
Electrostatic spinning is carried out using the graphite without polyoxometallate and is prepared into cathode pole piece, assembled battery is tested with embodiment 1.
Comparative example 2
Cathode pole piece is prepared into using traditional lithium-ion battery cathode pole piece production technology, assembled battery is tested with embodiment 1.
By above-described embodiment 1-4 and comparative example, gained battery does AC internal Resistance test, the results detailed in Table:
AC internal Resistance comparison can be seen that from table, is prepared into using the composite material of electrostatic spinning polyoxometallic acid lithium salts and graphite Cathode pole piece internal resistance be less than without polyoxometallic acid lithium salts pole piece, the internal resistance again smaller than conventional graphite as negative battery.

Claims (4)

1. a kind of preparation method of electrostatic spinning lithium ion battery negative electrode, which is characterized in that include the following steps:
(1) polyoxometallic acid lithium salts is dissolved in deionized water, forms polyoxometallic acid lithium salt solution;
(2) graphite is added in polyoxometallic acid lithium salt solution, and surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added, it is aqueous viscous Agent LA13x is met, spinning solution is formed;
(3) spinning solution is fitted into electrostatic spinning machine and carries out spinning, receiver board is copper foil, spinning head be it is multigroup, spinning head with The distance of receiver board is 0.1-8cm;Voltage is 16-20KV;Jet speed is 0.1-0.3mL/S, and strand is fine and close and uniform to be glued It is connected on copper foil, then the copper foil for being bonded with strand is dried, the negative pole piece of battery is made.
2. a kind of preparation method of electrostatic spinning lithium ion battery negative electrode according to claim 1, it is characterised in that: In the step (3), copper foil is driven using coating machine, and the transmission speed of coating machine adjusts phase with the jet speed of electrostatic spinning machine Adaptation.
3. a kind of preparation method of electrostatic spinning lithium ion battery negative electrode according to claim 1, it is characterised in that: In the step (3), spinning head is 5cm at a distance from receiver board;Voltage is 18KV;Jet speed is 0.2mL/S.
4. a kind of preparation method of electrostatic spinning lithium ion battery negative electrode according to claim 1, it is characterised in that: The polyoxometallic acid lithium salts is Li3XY12O40, Li4XY12O40One or more of mixture, wherein:X refers to P, Si two Any one in kind element;Y refers to any one in two kinds of elements of Mo, W.
CN201810318710.7A 2018-04-11 2018-04-11 A kind of preparation method of electrostatic spinning lithium ion battery negative electrode Pending CN108735976A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110323410A (en) * 2019-05-24 2019-10-11 宁波中车新能源科技有限公司 A kind of device and method preparing ultrathin electrodes
CN113299872A (en) * 2021-05-24 2021-08-24 天津森特新材料科技有限责任公司 Preparation method of lithium iron phosphate anode of lithium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683646A (en) * 2012-05-30 2012-09-19 焦作聚能能源科技有限公司 Preparation method of composite negative electrode material of lithium ion battery
CN103215665A (en) * 2013-04-27 2013-07-24 青岛大学 Compound annular electrode electrostatic spinning device
CN103311500A (en) * 2013-05-15 2013-09-18 深圳市慧通天下科技股份有限公司 Lithium-ion battery negative pole piece and production method
CN105226239A (en) * 2014-05-09 2016-01-06 纳米新能源(唐山)有限责任公司 Electrostatic applications is prepared lithium ion thin film electrode method, electrode and is comprised its battery
CN105977495A (en) * 2016-05-11 2016-09-28 中国东方电气集团有限公司 Preparation method of graphite paper for current collector of lithium-ion battery
WO2017159907A1 (en) * 2016-03-15 2017-09-21 동국대학교 산학협력단 Electrospun polyanionic positive electrode material-carbon nanofiber composite positive electrode active material for lithium secondary battery, and method for preparing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683646A (en) * 2012-05-30 2012-09-19 焦作聚能能源科技有限公司 Preparation method of composite negative electrode material of lithium ion battery
CN103215665A (en) * 2013-04-27 2013-07-24 青岛大学 Compound annular electrode electrostatic spinning device
CN103311500A (en) * 2013-05-15 2013-09-18 深圳市慧通天下科技股份有限公司 Lithium-ion battery negative pole piece and production method
CN105226239A (en) * 2014-05-09 2016-01-06 纳米新能源(唐山)有限责任公司 Electrostatic applications is prepared lithium ion thin film electrode method, electrode and is comprised its battery
WO2017159907A1 (en) * 2016-03-15 2017-09-21 동국대학교 산학협력단 Electrospun polyanionic positive electrode material-carbon nanofiber composite positive electrode active material for lithium secondary battery, and method for preparing same
CN105977495A (en) * 2016-05-11 2016-09-28 中国东方电气集团有限公司 Preparation method of graphite paper for current collector of lithium-ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110323410A (en) * 2019-05-24 2019-10-11 宁波中车新能源科技有限公司 A kind of device and method preparing ultrathin electrodes
CN110323410B (en) * 2019-05-24 2022-04-22 宁波中车新能源科技有限公司 Device and method for preparing ultrathin electrode
CN113299872A (en) * 2021-05-24 2021-08-24 天津森特新材料科技有限责任公司 Preparation method of lithium iron phosphate anode of lithium ion battery

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Application publication date: 20181102