CN108493453A - A kind of high-energy density LiFePO4 system soft-package battery and preparation method thereof - Google Patents
A kind of high-energy density LiFePO4 system soft-package battery and preparation method thereof Download PDFInfo
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- CN108493453A CN108493453A CN201810337190.4A CN201810337190A CN108493453A CN 108493453 A CN108493453 A CN 108493453A CN 201810337190 A CN201810337190 A CN 201810337190A CN 108493453 A CN108493453 A CN 108493453A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- 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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Abstract
The invention discloses a kind of high-energy density LiFePO4 system soft-package batteries and preparation method thereof, by enhancing the electric conductivity of LiFePO4 and mitigating the promotion of soft pack cell weight these two aspects realization energy density, introduce the carbon nanotube with one-dimensional linear structure, has larger draw ratio, form fine and close one-dimensional electric network, keep anode polarization small, electric conductivity improves, circulation is good, voltage platform is higher, while the losss of weight such as utter misery aluminium foil, utter misery copper foil, double-surface ceramics diaphragm, control guarantor's liquid coefficient realize that energy density is promoted.
Description
Technical field
The invention belongs to field of lithium, specifically, being related to a kind of high-energy density LiFePO4 system soft-package battery
And preparation method thereof.
Background technology
Lithium iron phosphate lithium battery is limited to the shortcomings of low material gram volume itself, poorly conductive at present, and LiFePO4 is made to exist
It is provided no advantage against in energy density.Active material ratio is relatively low in existing formula, common copper foil, aluminium foil conduction, caking property, light
Quantify poor, energy density is caused to be difficult to meet the needs of existing market is to power lithium iron phosphate battery.The present invention is by ferric phosphate
Lithium battery energy density is promoted to 176Wh/Kg, and significant effect is promoted to energy density.
Because of LiFePO 4 material poorly conductive itself and aluminium foil bad adhesion, more conductive black, PVDF is needed to change
It is kind, the ratio of crucial active material in formula is thus had compressed, capacity boost is difficult；Aluminium foil, diaphragm, electrolyte weight simultaneously
Amount also limits the promotion of energy density；LiFePO4 soft pack cell energy density is in 128Wh/kg-150Wh/kg at present, with three
First material system, which is compared, does not have energy density advantage.
In view of this special to propose the present invention.
Invention content
The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art and provide a kind of high-energy density ferric phosphate
Lithium system soft-package battery and preparation method thereof, in order to solve the above technical problems, the present invention is using the basic conception of technical solution：
A kind of high-energy density LiFePO4 system soft-package battery, including aluminum plastic film shell, positive plate, negative plate, ceramics
Diaphragm, electrolyte, the positive plate is by the positive electrode including plus plate current-collecting body, clad anode collector, the negative plate packet
The negative material for including negative current collector, coating negative current collector, the ceramic diaphragm include PP/PE basement membranes, are coated in basement membrane two
The alumina powder ceramic layer in face, the plus plate current-collecting body is formed by coating 1-2um conductive blacks and 10-12um aluminium foils, described
Negative current collector is coating 1-2um conductive blacks and 6-8um copper foils composition.
Further, the mass component of the positive electrode includes the positive active material of 97.5%-98.5%, 0.2%-
1.0% nano-level conducting agent, the Kynoar of 1.0%-1.5%.
Further, the positive electrode by anode active material of phosphate iron lithium, the agent of one-dimentional structure nano-level conducting and gathers
Vinylidene forms, and the one-dimentional structure nano-level conducting agent is one kind in VGCF, single-walled carbon nanotube, multi-walled carbon nanotube
Or arbitrary combination.
Further, the negative electrode active material of the negative material is that the sub- silicon blending 80%-90% of 10%-20% oxidations is pure
The silicon-carbon cathode of artificial modified graphite.
Further, each component quality proportioning of the negative material is negative electrode active material：Conductive black:Carboxymethyl is fine
The plain sodium of dimension：Butadiene-styrene rubber=(95%-97%):(0.8-1.2%):(1.0-1.3%):(2.0-2.5%).
Further, the thickness of the PP/PE basement membranes is 14um, and the thickness of two sides ceramic coating is 8um, ceramic diaphragm
Overall thickness is 22um.
Further, the density of washing one's face of the positive plate is 0.32-0.34g/1000mm2, compacted density 2.3-2.8g/
cm3。
Such as a kind of above-mentioned preparation method of high-energy density LiFePO4 system soft-package battery, including positive dispensing, cathode
Dispensing, positive and negative anodes film-making, assembly and encapsulation, fluid injection and activation, chemical conversion, two envelopes, 7 steps, the positive and negative anodes flaking step are made
Any positive plates of the claims 1-7 and negative plate.
Further, the chemical conversion step is：It is melted into using high-temperature clamp, temperature is controlled at 60-70 DEG C, is melted into pressure
260-300KPa/m2, point three step formation chargings, three step forming currents are respectively 0.02C, 0.2C, 0.36C, charging time difference
For 10min, 60min, 100min, chemical conversion SOC factually border volume controlled in 78-82%.
Further, the two envelopes step is：Two envelopes vacuumize, and protect liquid coefficient in 4.55-4.70g/Ah.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art.
The present invention improves energy density by improving active material ratio in formula, and coating applies aluminium foil, the copper foil of layer of charcoal, drop
Low interface impedance between collector and positive and negative anodes main material is convenient for electronic conduction, pole piece electric conductivity enhancing, it is possible to reduce main
The dosage of conductive black in material, meanwhile, pole piece caking property can be increased by applying layer of charcoal, it is possible to reduce Kynoar in anode formula
Dosage, thus play the proportioning of positive and negative anodes active material of main function to improve and provide possibility；The carbon of one-dimentional structure
Nanotube draw ratio is big, can enhance pole piece electric conductivity, has electric conductivity more stronger than conductive black, reduces the proportioning of conductive agent,
And a kind of single conductive agent of addition, compared with three-dimensional conductive network is formulated type, introducing impurity is less, and side reaction is few, cost
It is low, and dispensing processes more time-saving and efficiency, conductive agent is more easy to disperse.Energy density is promoted in terms of weight, pole piece electric conductivity enhances,
Under the premise of ensureing security performance, thermal diffusivity is good, realizes ceramic diaphragm, collector lightweight.
The specific implementation mode of the present invention is described in further detail below in conjunction with the accompanying drawings.
Description of the drawings
A part of the attached drawing as the application, for providing further understanding of the invention, of the invention is schematic
Embodiment and its explanation do not constitute inappropriate limitation of the present invention for explaining the present invention.Obviously, the accompanying drawings in the following description
Only some embodiments to those skilled in the art without creative efforts, can be with
Other accompanying drawings can also be obtained according to these attached drawings.In the accompanying drawings：
Fig. 1 is the cycle percentage and cycle period functional arrangement of the embodiment of the present invention and comparative example battery.
It should be noted that these attached drawings and verbal description are not intended to the design model limiting the invention in any way
It encloses, but is that those skilled in the art illustrate idea of the invention by referring to specific embodiments.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in embodiment is clearly and completely described, following embodiment for illustrating the present invention, but
It is not limited to the scope of the present invention.
Embodiment one
Step S1, positive dispensing：1.5% Kynoar is dissolved in N-Methyl pyrrolidone, 6.0% is formed and is uniformly mixed
Sol solution, add 0.5% multi-walled carbon nanotube (MWCNT), stirring 2h adds 98% ferric phosphate after evenly mixing
Lithium stirs 4h, obtains anode sizing agent.
Step S2, cathode blending：1.0-1.3% sodium carboxymethylcelluloses are dissolved in deionized water, 4.0% is obtained and obtains peptization
Liquid, sequentially add 0.8-1.2% conductive blacks, the silicon-carbon cathode described above of 95%-97%, 2.0-2.5% butadiene-styrene rubber into
Row stirring, obtains negative electrode slurry.
Step S3, positive and negative anodes film-making：Positive and negative electrode slurry is uniformly coated on 12um utter miseries aluminium foil, 6um utter misery copper foils respectively
On, positive and negative electrode double spread density of washing one's face is respectively 0.33g/1000mm2、0.133g/1000mm2, toasted, roll-in, cross cutting.
The negative plate of the positive plate and 211*237.5mm of 208*233.5mm is made.
Step S4, assembly and encapsulation:Pole piece is folded by diaphragm-negative plate-diaphragm-positive plate-diaphragm ... cathode-diaphragm
Piece is good, 28 layers of anode, 29 layers of cathode.Naked battery core is subjected to top side seal, toasts 36h.
Step S5, fluid injection and activation:Baked battery core is injected into LiFePO4 electrolyte, reservoir quantity 302g, and is sealed in advance,
Place into 40 ± 3 DEG C of letting live of high temperature for 24 hours.
Step S6, chemical conversion：Activated battery core is melted on high-temperature clamp formation cabinet, and chemical conversion temperature is controlled at 60-70 DEG C,
It is melted into pressure 260-300KPa/m2, point three step formation chargings, forming current is respectively 0.02C, 0.2C, 0.36C, charging time
Respectively 10min, 60min, 100min, chemical conversion SOC factually border volume controlled in 78-82%.
Step S7, two envelopes：Normal temperature shelf 4h after chemical conversion, then two envelopes are molded to obtain single battery core, protect liquid coefficient in 4.55-
4.70g/Ah.Using 0.5C capacity as reference capacity, high-energy density LiFePO4 system soft-package battery is obtained.
Embodiment two
Step S1, positive dispensing：1.5% Kynoar is dissolved in N-Methyl pyrrolidone, 6.0% is formed and is uniformly mixed
Sol solution, add 0.1% single-walled carbon nanotube (SWCNT), stirring 2h adds 98.4% phosphoric acid after evenly mixing
Iron lithium stirs 4h, obtains anode sizing agent.
Step S2, cathode blending：1.0-1.3% sodium carboxymethylcelluloses are dissolved in deionized water, 4.0% is obtained and obtains peptization
Liquid, sequentially add 0.8-1.2% conductive blacks, the silicon-carbon cathode described above of 95%-97%, 2.0-2.5% butadiene-styrene rubber into
Row stirring, obtains negative electrode slurry.
Step S3, positive and negative electrode film-making：Positive and negative electrode slurry is uniformly coated on 12um utter miseries aluminium foil, 6um utter misery copper respectively
On foil, positive and negative electrode double spread density of washing one's face is respectively 0.33g/1000mm2、0.134g/1000mm2, toasted, roll-in, mould
It cuts.The negative plate of the positive plate and 211*237.5mm of 208*233.5mm is made.
Step S4, assembly and encapsulation:Pole piece is folded by diaphragm-negative plate-diaphragm-positive plate-diaphragm ... cathode-diaphragm
Piece is good, 28 layers of anode, 29 layers of cathode.Naked battery core is subjected to top side seal, toasts 36h.
Step S5, fluid injection and activation:Baked battery core is injected into LiFePO4 electrolyte, reservoir quantity 302g, and is sealed in advance,
Place into 40 ± 3 DEG C of letting live of high temperature for 24 hours.
Step S6, chemical conversion：Activated battery core is melted on high-temperature clamp formation cabinet, and chemical conversion temperature is controlled at 60-70 DEG C,
It is melted into pressure 260-300KPa/m2, point three step formation chargings, forming current is respectively 0.02C, 0.2C, 0.36C, charging time
Respectively 10min, 60min, 100min, chemical conversion SOC factually border volume controlled in 78-82%.
Step S7, two envelopes：Normal temperature shelf 4h after chemical conversion, then two envelopes are molded to obtain single battery core, protect liquid coefficient in 4.55-
4.70g/Ah.Using 0.5C capacity as reference capacity, high-energy density LiFePO4 system soft-package battery is obtained.
Comparative example
Step S1, positive dispensing：3.5% Kynoar is dissolved in N-Methyl pyrrolidone, 6.0% is formed and is uniformly mixed
Sol solution, add 2.5% conductive agent Super P, 1% conductive agent 350G, 1% crystalline flake graphite KS-15, stir 2h,
After evenly mixing, the LiFePO4 stirring 4h for adding 92%, obtains anode sizing agent.
Step S2, cathode blending：1.2% sodium carboxymethylcellulose is dissolved in deionized water, 4.0% is obtained and obtains sol solution,
It sequentially adds 1.8% conductive black, 94.5% pure artificial graphite, 2.5% butadiene-styrene rubber to be stirred, obtains negative electrode slurry.
Step S3, positive and negative electrode film-making：Positive and negative electrode slurry is uniformly coated on 12um optical aluminum foils, on 6um light copper foils respectively,
Positive and negative electrode double spread density of washing one's face is respectively 0.33g/1000mm2、0.166g/1000mm2, toasted, roll-in, cross cutting.System
Obtain the negative plate of the positive plate and 211*237.5mm of 208*233.5mm.
Step S4, assembly and encapsulation:Pole piece is folded by diaphragm-negative plate-diaphragm-positive plate-diaphragm ... cathode-diaphragm
Piece is good, 28 layers of anode, 29 layers of cathode.Naked battery core is subjected to top side seal, toasts 36h.
Step S5, fluid injection and activation:Baked battery core is injected into LiFePO4 electrolyte, reservoir quantity 290g, and is sealed in advance,
Place into 40 ± 3 DEG C of letting live of high temperature for 24 hours.
Step S6, chemical conversion：Activated battery core is melted on high-temperature clamp formation cabinet, and chemical conversion temperature is controlled at 60-70 DEG C,
It is melted into pressure 260-300KPa/m2, point three step formation chargings, forming current is respectively 0.02C, 0.2C, 0.36C, charging time
Respectively 10min, 60min, 100min, chemical conversion SOC factually border volume controlled in 78-82%.
Step S7, two envelopes：Normal temperature shelf 4h after chemical conversion, then two envelopes are molded to obtain single battery core, protect liquid coefficient in 4.55-
4.70g/Ah.Using 0.5C capacity as reference capacity, comparative example battery is obtained.
Above-described embodiment and comparative example battery energy density contrast table such as following table：
It, can from above-mentioned table and figure referring to the cycle percentage of Fig. 1 embodiments and comparative example battery and cycle period functional arrangement
It learns, battery of the invention matches the energy density that can effectively promote battery, the cycle percentage of the longer battery of circulating cycle number
Difference is bigger, and the present invention obviously can promote battery performance compared with the prior art.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, it is right according to the technical essence of the invention as long as being the content without departing from technical solution of the present invention
Any simple modification, equivalent change and modification made by above example, in the range of still falling within the present invention program.
Claims (10)
1. a kind of high-energy density LiFePO4 system soft-package battery, which is characterized in that including aluminum plastic film shell, positive plate, bear
Pole piece, ceramic diaphragm, electrolyte, the positive plate are described by the positive electrode including plus plate current-collecting body, clad anode collector
Negative plate includes negative current collector, coats the negative material of negative current collector, and the ceramic diaphragm includes PP/PE basement membranes, coating
Alumina powder ceramic layer on basement membrane two sides, the plus plate current-collecting body is by coating 1-2um conductive blacks and 10-12um aluminium foil groups
At the negative current collector is coating 1-2um conductive blacks and 6-8um copper foils composition.
2. a kind of high-energy density LiFePO4 system soft-package battery according to claim 1, which is characterized in that it is described just
The mass component of pole material include the positive active material of 97.5%-98.5%, 0.2%-1.0% nano-level conducting agent,
The Kynoar of 1.0%-1.5%.
3. a kind of high-energy density LiFePO4 system soft-package battery according to claim 2, which is characterized in that it is described just
Pole material is made of anode active material of phosphate iron lithium, the agent of one-dimentional structure nano-level conducting and Kynoar, the one-dimensional knot
Structure nano-level conducting agent is VGCF, single-walled carbon nanotube, one kind in multi-walled carbon nanotube or arbitrary combination.
4. a kind of high-energy density LiFePO4 system soft-package battery according to claim 1, which is characterized in that described negative
The negative electrode active material of pole material is the silicon-carbon cathode that 10%-20% aoxidizes that sub- silicon blends the pure artificial modified graphites of 80%-90%.
5. a kind of high-energy density LiFePO4 system soft-package battery according to claim 4, which is characterized in that described negative
The each component quality proportioning of pole material is negative electrode active material：Conductive black:Sodium carboxymethylcellulose：Butadiene-styrene rubber=(95%-
97%):(0.8-1.2%):(1.0-1.3%):(2.0-2.5%).
6. a kind of high-energy density LiFePO4 system soft-package battery according to claim 1, which is characterized in that described
The thickness of PP/PE basement membranes is 14um, and the thickness of two sides ceramic coating is 8um, and the overall thickness of ceramic diaphragm is 22um.
7. a kind of high-energy density LiFePO4 system soft-package battery according to claim 1, which is characterized in that it is described just
The density of washing one's face of pole piece is 0.32-0.34g/1000mm2, compacted density 2.3-2.8g/cm3。
8. the preparation method of high-energy density LiFePO4 system soft-package battery, feature exist as described in claim 1-7 is any
In, including positive dispensing, cathode blending, positive and negative anodes film-making, assembly and encapsulation, fluid injection and activation, chemical conversion, two envelopes, 7 steps, institute
It states positive and negative anodes flaking step and any positive plates of the claims 1-7 and negative plate is made.
9. a kind of preparation method of high-energy density LiFePO4 system soft-package battery according to claim 8, feature
It is, the chemical conversion step is：It is melted into using high-temperature clamp, temperature is controlled at 60-70 DEG C, is melted into pressure 260-300KPa/m2,
Point three step formation chargings, three step forming currents are respectively 0.02C, 0.2C, 0.36C, the charging time be respectively 10min, 60min,
100min, chemical conversion SOC factually border volume controlled in 78-82%.
10. a kind of preparation method of high-energy density LiFePO4 system soft-package battery according to claim 8, feature
It is, the two envelopes step is：Two envelopes vacuumize, and protect liquid coefficient in 4.55-4.70g/Ah.
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| CN111211323A (en) * | 2020-01-13 | 2020-05-29 | 合肥国轩高科动力能源有限公司 | Soft package lithium ion battery of lithium iron phosphate system and preparation method thereof |
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Application publication date: 20180904 |