CN105591063A - High-power lithium iron phosphate battery and preparation method thereof - Google Patents

High-power lithium iron phosphate battery and preparation method thereof Download PDF

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Publication number
CN105591063A
CN105591063A CN201610149057.7A CN201610149057A CN105591063A CN 105591063 A CN105591063 A CN 105591063A CN 201610149057 A CN201610149057 A CN 201610149057A CN 105591063 A CN105591063 A CN 105591063A
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China
Prior art keywords
pole piece
lithium iron
iron phosphate
coating
hard carbon
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CN201610149057.7A
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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 CN201610149057.7A priority Critical patent/CN105591063A/en
Publication of CN105591063A publication Critical patent/CN105591063A/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
    • 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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

A high-power lithium iron phosphate battery is composed of a positive pole piece, a negative pole piece, a ceramic diaphragm, tabs, power rate type electrolyte and a metal shell. Netty aluminum foil is adopted in a current collector of the positive pole piece, and the surface of the netty aluminum foil is sequentially coated with lithium iron phosphate slurry and a lithium metaaluminate coating. Etched copper foil is adopted in the negative pole piece, silicon and coating hard carbon composite slurry of silicon are sequentially deposited on the surface of the etched copper foil, and multi-tab structures are adopted in the positive tab and the negative tab. The high-power lithium iron phosphate battery is characterized in that the positive pole piece and the negative pole piece are connected with the tabs in a welded manner, and the surfaces of the joints are coated with tab glue. Due to the fact that the netty aluminum foil current collector is adopted, the contact probability of active substances and the current collector is improved, and the internal resistance of the current collector is reduced. Meanwhile, the transmission rate of lithium irons in the charge and discharge process is increased due to the high lithium iron conductivity in the lithium metaaluminate coating. Meanwhile, a hard carbon composite is adopted in a negative electrode, and therefore the large-rate discharge capacity of the lithium irons can be improved, and the heat radiation performance and safety performance of the lithium iron battery can be improved.

Description

A kind of high power lithium iron phosphate cell and preparation method thereof
Technical field
The invention belongs to lithium ion battery preparation field, specifically by applying active material at modification collection liquid surfacePrepare both positive and negative polarity pole piece, and prepare ferric phosphate lithium ion battery.
Background technology
Ferric phosphate lithium ion battery is a kind of novel energy-storing power supply growing up in recent years, and with its cycle lifeGood, cheap, advantages of environment protection and be subject to people's favor, and be widely used in pure electric automobile, hybrid electric vehicle,Electric tool and energy storage field thereof. But along with the increase in demand that people fill soon, put soon lithium ion battery, require high-power lithiumIon battery is to meet the demand in market, and the high power lithium ion cell released is in the market a 20C left side in multiplying power conventionallyThe right side, can cause the loss of energy density, such as patent (CN104577130A) discloses for improving the power of lithium ion batteryFlexible package high power lithium iron phosphate electrokinetic cell, although improve the high rate performance of lithium ion battery by primary coat technology, depositsIn shortcomings such as energy density reduction and cycle life reductions thereof, in improving the large high rate performance of lithium ion battery, take into accountIt is very necessary that energy density and cycle performance seem, and can Industry Promotion.
Summary of the invention
The present invention is just based on the shortcoming such as current LiFePO4 high rate performance is poor, by adopting netted aluminium foil and etching Copper FoilCollector, and adopt multi pole ears mode to improve the high rate performance of lithium ion battery, the while can be taken into account again the energy of lithium ion batteryDensity and cycle performance, improve the combination property of lithium ion battery.
Technical scheme of the present invention is achieved in the following ways: a kind of high power lithium iron phosphate cell, and by the anodal utmost pointSheet, cathode pole piece, ceramic diaphragm, lug, merit rate electrolyte and metal shell composition, described anode pole piece collector is adoptedUse netted aluminium foil, apply successively LiFePO4 slurry and lithium metaaluminate coating on its surface; Cathode pole piece adopts etching Copper Foil,Its surface is depositing silicon and coating hard carbon composite mortar thereof successively, and positive and negative electrode lug all adopts multi pole ears structure; It is characterized in that:Described positive and negative electrode pole piece and lug are by being welded to connect, and its surface, junction is coated with tab.
The slurry coating area of described netted aluminium foil adopts network structure, and its mesh size is 100 ~ 1000 μ m, mesh rateBe 10 ~ 50%, tab welding district adopts without mesh aluminium foil, and the thickness of aluminium foil is 15 ~ 40 μ m.
Preparation method of the present invention: comprise the following steps:
1), make anode pole piece: get netted aluminium foil sulfuric acid it is carried out to etching: the degree of depth of etching is 0.5 ~ 2 μ m, between etched lineApart from being 1 ~ 5mm, etch areas surface is coated with LiFePO4 coating and lithium metaaluminate coating successively, makes netted aluminium foil, phosphoric acidIron lithium layer, lithium metaaluminate coating layer thickness ratio are: 1:5 ~ 10:0.5 ~ 1;
2), make cathode pole piece: etching Copper Foil, Copper Foil adopt Mechanical Method carry out etching, the etching depth of Copper Foil is 0.5 ~ 2 μ m,Etched line spacing is 1 ~ 5mm, and etch areas surface depositing silicon and apply hard carbon composite mortar successively, and other region is without etching,Finally obtain cathode pole piece;
Described depositing silicon is to adopt vapour deposition process depositing silicon.
The thickness of described Copper Foil, silicon, hard carbon layer is: 5 ~ 15:1:50 ~ 150.
The proportioning of described coating hard carbon composite mortar is: hard carbon: PVDF binding agent: SP conductive agent=90:5:5, and by being coated withCopper foil surface is applied hard carbon composite mortar by cloth machine.
3), the coat of anode pole piece and cathode pole piece is welded with aluminium foil lug at its lug place respectively after dry and nickel closesGold lug, and be coated with tab on surface, positive and negative electrode tab welding place, then add ceramic diaphragm, lug, the electrolysis of merit rateLiquid and metal shell make high power lithium iron phosphate cell.
Beneficial effect of the present invention: 1, adopt netted aluminium foil, not only can improve connecing between active material and collectorTouch area, reduce internal resistance, and therefore improve the large multiplying power discharging ability of lithium ion battery; Meanwhile, adopt netted aluminum foil current collectorCan improve the utilization rate of active material, and therefore improve the energy density of lithium ion battery. 2, adopt etching Copper Foil, due to copperEtching has been carried out on paper tinsel surface, adopts chemical gas-phase method can make silicon more easily be deposited on its surface, simultaneously the silicon materials of high power capacityCan be used as again negative electrode active material and improve negative material capacity, and adopt sedimentation can fall at the silicon of collection liquid surface depositionThe expansion rate of low silicon materials in charge and discharge process, and improve the energy density of cycle performance and lithium ion battery. 3, positive and negativeUtmost point pole piece and lug place apply the thermal diffusivity at the lug place under the large multiplying power discharging condition that tab can improve lithium ion batteryEnergy and security performance thereof.
Brief description of the drawings
Fig. 1 is discharge voltage-capability retention curve map of embodiment;
Fig. 2 is discharge voltage-capability retention curve map of comparative example.
Detailed description of the invention
Embodiment 1:
The netted aluminium foil (mesh size is 500 μ m, and mesh rate is 30%) of getting 20 μ m carries out etching with sulfuric acid to it: etching darkDegree is 0.5 ~ 2 μ m, and etched line spacing is 1 ~ 5mm, and etch areas surface is coated with 160 μ m LiFePO4 coatings successively, has been driedAfter finishing, apply 16 μ m lithium metaaluminate coatings, obtain anode pole piece, and at its lug place welding aluminium foil lug;
Adopt Mechanical Method to carry out etching (etching depth of its Copper Foil is 1 μ m, and etched line spacing is 2mm) to 10 μ m Copper Foils, adoptVapour deposition process is at etching Copper Foil surface deposition silicon steam, and its deposit thickness is 1 μ m, obtains pole piece B; Configure hard carbon slurry simultaneously(hard carbon: PVDF binding agent: SP conductive agent=90:5:5), applies hard carbon slurry by coating machine by pole piece B surface afterwards, appliesThickness 120 μ m, finally obtain cathode pole piece, and at its lug place welding nickel alloy lug. Discharge voltage-capacity of embodiment 1Conservation rate curve map as shown in Figure 1.
Embodiment 2:
Getting thickness is the netted aluminium foil of 15 μ m (mesh size is 100 μ m, and mesh rate is 50%), and is 75 μ at its surperficial coating thicknessM lithium-iron phosphate active material, applying 7.5 μ m lithium metaaluminate layers on its surface, finally obtains anode pole piece after being dried, andAt its lug place welding aluminium foil lug.
(etching depth of its Copper Foil is 0.5 μ m, and etched line spacing is to adopt Mechanical Method to carry out etching to 5 μ m Copper Foil A1mm), adopt afterwards vapour deposition process at etching Copper Foil surface deposition silicon steam, its deposit thickness is 1 μ m, obtains pole piece B; WithTime configure hard carbon slurry (hard carbon: PVDF binding agent: SP conductive agent=90:5:5), by coating machine, pole piece B surface is applied afterwardsHard carbon slurry, coating thickness 50 μ m, finally obtain cathode pole piece, and at its lug place welding nickel alloy lug.
Embodiment 3:
Getting thickness is the netted aluminium foil of 40 μ m (mesh size is 100 μ m, and mesh rate is 50%), and is 400 at its surperficial coating thicknessμ m lithium-iron phosphate active material, applying 40 μ m lithium metaaluminate layers on its surface, finally obtains anode pole piece after being dried, andAt its lug place welding aluminium foil lug.
Adopt Mechanical Method to carry out etching (etching depth of its Copper Foil is 2 μ m, and etched line spacing is 5mm) to 15 μ m Copper Foil A,Adopt afterwards vapour deposition process at etching Copper Foil surface deposition silicon steam, its deposit thickness is 1 μ m, obtains pole piece B; Configuration simultaneouslyHard carbon slurry (hard carbon: PVDF binding agent: SP conductive agent=90:5:5), applies hard carbon slurry by coating machine by pole piece B surface afterwardsMaterial, coating thickness 150 μ m, finally obtain cathode pole piece, and at its lug place welding nickel alloy lug.
The anode pole piece prepared using embodiment 1-3 afterwards, cathode pole piece are respectively as the both positive and negative polarity utmost point of lithium ion batterySheet, electrolyte uses LiPF6For electrolyte, concentration is 1.3mol/L, and the EC that volume ratio is 1:1 and DEC are solvent, and barrier film usesCelgard2400 ceramic membrane, utilizes prior art to prepare 5Ah soft-package battery A1, A2, A3.
Battery as a comparison: the Copper Foil taking 12 μ m is prepared negative pole as negative current collector and at its surface coating DelaniumPole piece, taking the aluminium foil of 20 μ m as plus plate current-collecting body, and applies LiFePO4 on its surface and prepares anode pole piece, and electrolyte usesLiPF6For electrolyte, concentration is 1.3mol/L, and the EC that volume ratio is 1:1 and DEC are solvent, and barrier film uses Celgard2400Ceramic membrane, utilizes prior art to prepare 5Ah soft-package battery B.
Under condition taking multiplying power as 0.3C, charge afterwards, to discharge under 0.5C, 1.0C, 2.0C, 4.0C, 8.0C condition, surveyTry high rate performance and the cycle performance of its battery. Test result is as shown in table 1.
Table 1: adopt embodiment and comparative example to make multiplying power/cycle performance comparison of lithium ion battery
As can be seen from Table 1, the high rate performance of the battery that embodiment prepares is obviously better than comparative example, and it is former because adopt nettedAluminium foil improves the contact area of its active material and collector, thereby reduces its internal resistance, improves its high rate performance, simultaneously the negative pole utmost pointHard carbon material in sheet has larger interlamellar spacing, and the embedding that is conducive to lithium ion goes out, and improves the transfer rate of lithium ion.
The energy density comparison of table 2, embodiment and comparative example
As can be seen from Table 2, the energy density of the battery that embodiment prepares is obviously better than comparative example, its former because, reticulated aluminumPaper tinsel increases the utilization ratio of active material, thereby improves the energy density of its lithium ion battery. If Fig. 2 is the electric discharge electricity of comparative examplePressure-capability retention curve map.

Claims (6)

1. a high power lithium iron phosphate cell, by anode pole piece, cathode pole piece, ceramic diaphragm, lug, merit rate electrolyteWith metal shell composition, described anode pole piece collector adopts netted aluminium foil, applies successively LiFePO4 slurry on its surfaceWith lithium metaaluminate coating; Cathode pole piece adopts etching Copper Foil, on its surface successively depositing silicon and apply hard carbon composite mortar,Positive and negative electrode lug all adopts multi pole ears structure; It is characterized in that: described positive and negative electrode pole piece and lug be by being welded to connect, itsSurface, junction is coated with tab.
2. a kind of high power lithium iron phosphate cell according to claim 1, is characterized in that: the slurry of described netted aluminium foilMaterial coating area adopts network structure, and its mesh size is 100 ~ 1000 μ m, and mesh rate is 10 ~ 50%, and tab welding district adopts without netHole aluminium foil, and the thickness of aluminium foil is 15 ~ 40 μ m.
3. a preparation method for a kind of high power lithium iron phosphate cell according to claim 1, is characterized in that: compriseFollowing steps:
1), make anode pole piece: get netted aluminium foil sulfuric acid it is carried out to etching: the degree of depth of etching is 0.5 ~ 2 μ m, between etched lineApart from being 1 ~ 5mm, etch areas surface is coated with LiFePO4 coating and lithium metaaluminate coating successively, makes netted aluminium foil, phosphoric acidIron lithium layer, lithium metaaluminate coating layer thickness ratio are: 1:5 ~ 10:0.5 ~ 1;
2), make cathode pole piece: etching Copper Foil, Copper Foil adopt Mechanical Method carry out etching, the etching depth of Copper Foil is 0.5 ~ 2 μ m,Etched line spacing is 1 ~ 5mm, and etch areas surface depositing silicon and apply hard carbon composite mortar successively, and other region is without etching,Finally obtain cathode pole piece;
3), the coat of anode pole piece and cathode pole piece is welded with aluminium foil lug and the nickel alloy utmost point at its lug place respectively after being driedEar, and be coated with tab on surface, positive and negative electrode tab welding place, then add ceramic diaphragm, lug, merit rate electrolyte andMetal shell makes high power lithium iron phosphate cell.
4. the preparation method of a kind of high power lithium iron phosphate cell according to claim 3, is characterized in that: described stepRapid 2) depositing silicon is to adopt vapour deposition process depositing silicon.
5. the preparation method of a kind of high power lithium iron phosphate cell according to claim 3, is characterized in that: described stepRapid 2) proportioning of coating hard carbon composite mortar is: hard carbon: PVDF binding agent: SP conductive agent=90:5:5, by coating machine by copperPaper tinsel surface applies hard carbon composite mortar.
6. the preparation method of a kind of high power lithium iron phosphate cell according to claim 3, is characterized in that: described stepRapid 2) thickness of Copper Foil in, silicon, hard carbon layer is: 5 ~ 15:1:50 ~ 150.
CN201610149057.7A 2016-03-16 2016-03-16 High-power lithium iron phosphate battery and preparation method thereof Pending CN105591063A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229447A (en) * 2016-08-10 2016-12-14 东莞永蓝电子科技有限公司 A kind of lithium ion battery
CN110635138A (en) * 2019-08-02 2019-12-31 河南平煤国能锂电有限公司 Lithium ion battery pole piece and manufacturing method thereof
CN113921895A (en) * 2021-09-29 2022-01-11 东方电气集团科学技术研究院有限公司 Lithium iron phosphate battery and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103354284A (en) * 2013-07-02 2013-10-16 南通宁远自动化科技有限公司 Metal foil perforating machine
CN103531815A (en) * 2013-10-25 2014-01-22 深圳清华大学研究院 Perforated foil used for current collector and its making method
CN105244506A (en) * 2015-10-15 2016-01-13 青岛领军节能与新材料研究院 Lithium-ion battery material and lithium-ion battery structure and preparation method of lithium-ion battery material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103354284A (en) * 2013-07-02 2013-10-16 南通宁远自动化科技有限公司 Metal foil perforating machine
CN103531815A (en) * 2013-10-25 2014-01-22 深圳清华大学研究院 Perforated foil used for current collector and its making method
CN105244506A (en) * 2015-10-15 2016-01-13 青岛领军节能与新材料研究院 Lithium-ion battery material and lithium-ion battery structure and preparation method of lithium-ion battery material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229447A (en) * 2016-08-10 2016-12-14 东莞永蓝电子科技有限公司 A kind of lithium ion battery
CN110635138A (en) * 2019-08-02 2019-12-31 河南平煤国能锂电有限公司 Lithium ion battery pole piece and manufacturing method thereof
CN113921895A (en) * 2021-09-29 2022-01-11 东方电气集团科学技术研究院有限公司 Lithium iron phosphate battery and preparation method thereof

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Application publication date: 20160518