CN105633353A - Preparation method of positive pole piece of high-rate lithium-ion battery - Google Patents

Preparation method of positive pole piece of high-rate lithium-ion battery Download PDF

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Publication number
CN105633353A
CN105633353A CN201610147897.XA CN201610147897A CN105633353A CN 105633353 A CN105633353 A CN 105633353A CN 201610147897 A CN201610147897 A CN 201610147897A CN 105633353 A CN105633353 A CN 105633353A
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CN
China
Prior art keywords
pole piece
ion battery
preparation
positive pole
lithium
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Application number
CN201610147897.XA
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Chinese (zh)
Inventor
丁建民
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JIANGSU LENENG BATTERY CO Ltd
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JIANGSU LENENG BATTERY CO Ltd
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Priority to CN201610147897.XA priority Critical patent/CN105633353A/en
Publication of CN105633353A publication Critical patent/CN105633353A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • 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
    • H01M2004/028—Positive 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

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

Abstract

The invention provides a preparation method of a positive pole piece of a high-rate lithium-ion battery. The method is characterized by comprising the following steps: firstly, preparing a composite primer liquid; coating the surface of a nickel foam cathode current collector with the composite primer liquid by a gravure printing or spraying technology and drying the nickel foam cathode current collector to obtain a cathode primed piece; and coating the surface with cathode lithium iron phosphate slurry, and carrying out drying and roll-cutting procedures to prepare the positive pole piece. The prepared positive pole piece develops the advantages of high conductivity, high adhesive force and corrosion resistance of a priming coat and the advantage of low volume energy density of a mesh current collector; the cycle performance and the rate capability of the pole piece in the lithium-ion battery are greatly improved; meanwhile, the energy density of the battery is also improved; and the lithium-ion battery prepared from the pole piece is especially suitable for application in a hybrid electric vehicle.

Description

The preparation method of a kind of high multiplying power lithium ion battery anode pole piece
Technical field
The invention belongs to electrodes of lithium-ion batteries preparation field, apply primary coat liquid to improve the over-all properties of lithium ion battery at collection liquid surface specifically.
Background technology
Iron lithium phosphate is a kind of novel energy storage cell grown up in recent years, and with its safety performance height, have extended cycle life, advantages of environment protection become a kind of Novel power battery. But owing to the electroconductibility of iron lithium phosphate is poor, need in iron lithium phosphate, to adulterate some conductive agents to improve the conductivity of its material, and improve the conductivity of ion between its active material, and the conductivity between active material and current collector aluminum foil is not improved. Owing to iron lithium phosphate primary particle particle diameter is less, the contact of itself and aluminium foil surface is point cantact, and iron lithium phosphate active material and current collector aluminum foil bonding are poor, causes internal resistance and the polarization increase thereof of battery, and has influence on high rate performance, the cycle performance of battery.
Collector primary coat technology is a kind of new technique grown up in recent years, namely one layer of primary coat liquid containing conductive agent is applied at collection liquid surface, improve high rate performance and the cycle performance of battery, especially LiFePO 4 material material for low conductivity is especially obvious, there is coat-thickness makes the volume of electrode current collecting body take than increase simultaneously, reduce the loading of active substance, thus reduce the problem of the whole volume of battery. And metal foam can solve active substance as collector occupies than low shortcoming.
Owing to there is the three-dimensional pore space of porous in foamed metal, it is possible to make active substance be filled in this hole, instead of its surface can only be coated in as paper tinsel body collector. And after active substance is filled in the porous three-dimensional pore space in foamed metal Nei, not only increase filling ratio, and due to the three dimensional pore structures of foamed metal itself and porous be more conducive to current density be uniformly distributed with electrolyte permeability, be uniformly distributed, such that it is able to improve the active material utilization of lithium ion battery, the capacity of lithium ion battery plays and multiplying power discharging property. On the contrary, for metal foil, active substance can only be distributed in the surface of collector, the electric energy changing into chemical energy mainly passes to active substance by collector, active substance near collector and the active substance away from collector are widely different point mixing of electric energy, the closer to collector, also more even while that its electric energy distributed being more many, more away from collector, its electric energy distributed is more few. Can find out that the metal foil adopted due to affluxion body in lithium ion batteries result in lithium ion battery active substance input and output and the ununiformity of energy in conversion process, have influence on the raising of active material utilization. And the foamed metal of large-scale commercial has foam copper and nickel foam, the oxidizing potential of copper very low being not suitable for do plus plate current-collecting body, and the theoretical oxidizing potential of nickel is about 3.8V, close to the restriction voltage 3.65V of iron lithium phosphate, but due to the irrational state of nickel surface in practical application, its oxidizing potential is caused to reduce, so pure foam nickel be not applied in the iron lithium phosphate system lithium cell of commercialization, it is necessary to the demand of lithium ion battery can be met in its electroplating surface layer of substance.
Summary of the invention
Can poor, the problem such as cycle performance general and energy density is not high for current electrodes of lithium-ion batteries poor adhesion and battery rate thereof, the present invention provides a kind of while improving electrodes of lithium-ion batteries adhesive power, lithium ion battery high rate performance, can improve again the preparation method of the battery positive pole piece of lithium ion battery energy density.
The technical scheme of the present invention is achieved in the following ways: the preparation method of a kind of high multiplying power lithium ion battery anode pole piece, with parts by weight, it is characterized in that: first configure combined bottom masking liquid, it is coated in foam nickel anode collection liquid surface afterwards by intaglio printing or spraying technology, coating thickness is 1 ��m, dry obtained positive pole primary coat pole piece, then at its surface-coated positive pole iron lithium phosphate slurry, and prepare anode pole piece through drying, roll-in, slicing process.
Described combined bottom masking liquid is by binding agent, conductive polymers, doping agent, conductive agent, the forming of organic solvent; Its ratio is: binding agent: conductive polymers: doping agent: conductive agent: organic solvent=5 ~ 50:5 ~ 10:0.1 ~ 1:1 ~ 20:100.
Described binding agent is polyvinylidene difluoride (PVDF) (PVDF), and conductive polymers is the one in polyaniline, polypyrrole, Polythiophene, and doping agent is Phenylsulfonic acid, and organic solvent is N-Methyl pyrrolidone (NMP).
The porosity of described nickel foam is 60 ~ 90%.
The useful effect of the present invention: 1) adopt modified nickel foam, after active substance is filled in the porous three-dimensional pore space in foamed metal Nei, not only increase filling ratio, and due to the three dimensional pore structures of foamed metal itself and porous be more conducive to current density be uniformly distributed with electrolyte permeability, be uniformly distributed, such that it is able to improve the active material utilization of lithium ion battery, it is to increase the capacity of lithium ion battery and multiplying power discharging property. The heat balance in charge and discharge process can be improved again, it is to increase the performances such as the circulation ratio of its battery simultaneously. 2) adopt described in composite guide electro-hydraulic, owing to conductive liquid having conductive polymers, it is possible to improve the transfer rate of lithium ion and electronics thereof, it is to increase the big multiplying power discharging ability of its material. 3) modified nickel foam prevents electrolytic solution corrosive deposit relative to nickel foam owing to having in its surface-coated, can reduce the collector internal resistance increase owing to electrolytic solution and primary coat corrosion thereof cause, and therefore improves the chemical property of lithium ion battery.
Accompanying drawing explanation
The structural representation of Fig. 1, anode pole piece of the present invention.
In figure: 11 is active material layer, 12 is undercoat, and 13 is reticulated collectors.
Embodiment
The preparation method of a kind of high multiplying power lithium ion battery anode pole piece, first combined bottom masking liquid is configured, it is coated in foam nickel anode collection liquid surface afterwards by intaglio printing or spraying technology, dry obtained positive pole primary coat pole piece, again at its surface-coated positive pole iron lithium phosphate slurry, and make anode pole piece through drying, roll-in, slicing process.
Embodiment 1:
1, the consisting of of combined bottom masking liquid: take 30gPVDF binding agent, 8g polyaniline, 0.5g Phenylsulfonic acid, 10gSP conductive agent and 100gNMP organic solvent successively and put in ultrasonic disperse machine, and ultrasonic disperse evenly obtains oiliness combined bottom masking liquid;
2, the modified nickel foam that porosity is 80% is chosen, and adopt intaglio printing technology to be coated in nickel foam by above-mentioned oiliness combined bottom masking liquid, coating thickness is 1 ��m, after dry, again by coating machine at its surface-coated iron lithium phosphate slurry, and obtain anode pole piece through drying, roll-in, section.
Embodiment 2:
1, the consisting of of combined bottom masking liquid, takes 5.0gPVDF binding agent, 5.0g polyaniline, 0.1g Phenylsulfonic acid, 1.0gSP conductive agent and 100gNMP organic solvent thereof successively and puts in ultrasonic disperse machine, and ultrasonic disperse evenly obtains oiliness combined bottom masking liquid;
2, the modified nickel foam that porosity is 60% is chosen, and adopt intaglio printing technology to be coated in nickel foam by above-mentioned oiliness combined bottom masking liquid, coating thickness is 1 ��m, after dry, again by coating machine at its surface-coated iron lithium phosphate slurry, and obtain anode pole piece through dry, section, roll-in.
Embodiment 3:
1, the consisting of of combined bottom masking liquid, takes 50gPVDF binding agent, 10g polyaniline, 1.0g Phenylsulfonic acid, 20gSP conductive agent and 100gNMP organic solvent thereof successively and puts in ultrasonic disperse machine, and ultrasonic disperse evenly obtains oiliness combined bottom masking liquid;
2, the modified nickel foam that porosity is 90% is chosen, and adopting intaglio printing technology to be coated in nickel foam by above-mentioned oiliness combined bottom masking liquid, coating thickness is 1 ��m, after dry, again by coating machine at its surface phosphoric acid iron lithium slurry, and obtain anode pole piece through drying, roll-in, section.
Comparative example 1:
Step 1 is identical with embodiment 1, and difference is that other is identical with embodiment 1 without primary coat liquid composition in step 1 for only having binding agent, conductive agent, solvent.
Comparative example 2:
Step 1 is identical with embodiment 1, and difference is in step 2 collector and selects aluminium foil.
Comparative example 3:
Adopt iron lithium phosphate slurry to be coated in 80% nickel foam, and obtain anode pole piece through drying, roll-in, section.
1) physical and chemical performance test:
The anode pole piece choosing embodiment 1 ~ 3 and comparative example 1 ~ 3 respectively tests its pole piece adhesive power and imbibition liquid-keeping property thereof.
Adhesive power testing standard: choose 5mm �� 30mm anode pole piece and be pasted on 3M adhesive tape, adopts tensilon to test the adhesive power of its pole piece afterwards.
Fig. 1 is that embodiment prepares the pole piece structure iron, and wherein 11 is active material layer, and 12 is undercoat, and 13 is collector nickel foam.
Table 1, embodiment compare with the physical and chemical performance of comparative example
As can be seen from Table 1, embodiment is compared with comparative example, it is largely increased in material imbibition liquid-keeping property and pole piece adhesive power thereof, it is that collector nickel foam selected by embodiment has higher porosity and the contact area bigger with active substance thereof on the one hand, thus improve the imbibition liquid-keeping property of material on electrolyte, simultaneously owing to comparative example active substance and collector are point cantact, and embodiment is owing to adopting primary coat technology to make its active substance and undercoat be that face contacts, thus improve the adhesive power of pole piece.
2) electrochemical property test: prepare the pole piece using embodiment 1 ~ 3 and comparative example 1 ~ 3 as plus plate current-collecting body, iron lithium phosphate is as positive pole, and using synthetic graphite as negative material, adopts LiPF6/ EC+DEC (volume ratio 1: 1) is electrolytic solution, and Celgard2400 film is barrier film, prepares high rate performance and cycle performance that 5AH soft-package battery A1, A2, A3, B1, B2, B3 test its soft-package battery, and calculates energy density.
The high rate performance of table 2, embodiment and comparative example battery, cycle performance and energy density thereof compare
As can be seen from Table 2, embodiment owing to increasing by one layer of undercoat between active substance and collector, thus make the point cantact between active substance with collector turn into face and contact, and reduces its pole piece internal resistance, and improves the high rate performance of its battery. Simultaneously owing to electrolytic solution and collector can be kept apart by undercoat, prevent battery in long-term working cycle electrolytic solution to the corrosion of collector, it is to increase the structural stability of its battery, and therefore improve the cycle performance of battery. And embodiment collector used is foam hole dress nickel foam, between its nickel foam can holding portion active substance, thus the energy density of its material can be improved again.

Claims (4)

1. the preparation method of a high multiplying power lithium ion battery anode pole piece, with parts by weight, it is characterized in that: first configure combined bottom masking liquid, it is coated in foam nickel anode collection liquid surface afterwards by intaglio printing or spraying technology, dry obtained positive pole primary coat pole piece, again at its surface-coated positive pole iron lithium phosphate slurry, and prepare anode pole piece through drying, roll-in, slicing process.
2. a kind of high multiplying power lithium ion battery anode pole piece according to claim 1 and preparation method, it is characterised in that: described combined bottom masking liquid is by binding agent, conductive polymers, doping agent, conductive agent, the forming of organic solvent; Its ratio is: binding agent: conductive polymers: doping agent: conductive agent: organic solvent=5 ~ 50:5 ~ 10:0.1 ~ 1:1 ~ 20:100.
3. the preparation method of a kind of high multiplying power lithium ion battery anode pole piece according to claim 2, it is characterized in that: described binding agent is polyvinylidene difluoride (PVDF) (PVDF), conductive polymers is the one in polyaniline, polypyrrole, Polythiophene, doping agent is Phenylsulfonic acid, and organic solvent is N-Methyl pyrrolidone (NMP).
4. the preparation method of a kind of high multiplying power lithium ion battery anode pole piece according to claim 1, it is characterised in that: the porosity of described nickel foam is 60 ~ 90%.
CN201610147897.XA 2016-03-16 2016-03-16 Preparation method of positive pole piece of high-rate lithium-ion battery Pending CN105633353A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109309192A (en) * 2017-07-28 2019-02-05 宁德时代新能源科技股份有限公司 Electrode slice and electrochemical energy storage device
CN110718674A (en) * 2019-10-15 2020-01-21 宁波铵特姆新能源科技有限公司 Current collector conductive coating and preparation method thereof
CN112201848A (en) * 2020-09-03 2021-01-08 华中科技大学 Solid electrolyte, composite integrated anode, integrated battery and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102677091A (en) * 2012-06-06 2012-09-19 哈尔滨工业大学 Preparation method for palladium modified electrode with base body formed by para-toluenesulfonic acid mixed with polypyrole
CN104852013A (en) * 2015-03-17 2015-08-19 中国科学院广州能源研究所 Preparation method of three-dimensional electrode slice based on aqueous adhesive

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102677091A (en) * 2012-06-06 2012-09-19 哈尔滨工业大学 Preparation method for palladium modified electrode with base body formed by para-toluenesulfonic acid mixed with polypyrole
CN104852013A (en) * 2015-03-17 2015-08-19 中国科学院广州能源研究所 Preparation method of three-dimensional electrode slice based on aqueous adhesive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109309192A (en) * 2017-07-28 2019-02-05 宁德时代新能源科技股份有限公司 Electrode slice and electrochemical energy storage device
CN110718674A (en) * 2019-10-15 2020-01-21 宁波铵特姆新能源科技有限公司 Current collector conductive coating and preparation method thereof
CN112201848A (en) * 2020-09-03 2021-01-08 华中科技大学 Solid electrolyte, composite integrated anode, integrated battery and preparation method thereof

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Application publication date: 20160601