CN105932334A - High-energy lithium ion battery and fabrication method thereof - Google Patents
High-energy lithium ion battery and fabrication method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title abstract 2
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- 239000010416 ion conductor Substances 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000004513 sizing Methods 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000005030 aluminium foil Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910018869 La0.5Li0.5TiO3 Inorganic materials 0.000 claims description 3
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 3
- 229910011201 Li7P3S11 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 20
- 239000010410 layer Substances 0.000 description 17
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910021190 Li0.5TiO3 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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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
- H01M10/058—Construction or manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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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- 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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Abstract
The invention discloses a high-energy lithium ion battery and a fabrication method thereof. By coating the surface of lithium metal with a nanometer lithium fast ion conductor ceramic layer, side reaction between the lithium metal and an electrolyte during charging and discharging is prevented, metallic lithium dendrite is also prevented from forming and growing, meanwhile, the resistance of a protection film to lithium ion migration is reduced, the impedance increase of the protection film on the battery is substantially reduced, so that high-energy density output can be achieved while the cycle safety of the battery is ensured and the service lifetime of the battery is prolonged, and the energy demand of electric vehicle driving range is met.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of high energy lithium ion cell and preparation method thereof.
Background technology
Along with scientific and technological progress, the miniaturization of various electrical equipment, thin trend need, and people are in the urgent need to a kind of high energy density cells.The negative pole of traditional lithium-ion battery uses graphite to be negative pole, graphite not only theoretical capacity low (only 372mAh/g), and irreversible capacity loss is big first, it is impossible to become high energy density cells.And the theoretical capacity of lithium metal reaches 3860mAh/g, and the exchange current density of lithium electrode is big, it is little to polarize, and is preferable battery material.But the actual application of lithium electrode there is also some problems needing to solve, dendrite problems and the consistency problem with electrolyte.
Lithium metal is high with the reactivity of general electrolytic liquid, needle-like dendrite is often formed on cathode of lithium surface, if dendrite undue growth and and positive contact, internal short-circuit then can occur, cause safety problem, have a strong impact on the cycle life of lithium metal battery, it is suppressed that the actual application of high-energy-density metal lithium battery.In order to make high-energy-density metal lithium battery obtain preferable cycle life, it is necessary to reduce the reactivity of lithium metal and electrolyte, but can not thorough passive metal lithium, cause and can not realize high discharge current density.
For the modification of lithium anode also relates to the example of surface-coated protective layer; but it mostly is the protective layer not having lithium ion conductive; although improving the surface topography of lithium anode; but greatly increase internal battery impedance; have impact on battery performance to play, limit the lithium anode actual application in lithium ion battery.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium ion battery and preparation method thereof, it is intended to solve existing lithium ion battery be still difficult to meet be actually needed, internal battery impedance is big and cycle life is short problem.
Technical scheme is as follows:
A kind of preparation method of high energy lithium ion cell, wherein, including step:
A, join organic solvent is sufficiently mixed according to 85～90:10～15 mass ratios by nanometer lithium fast-ionic conductor ceramics, bonding agent and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, after drying, roll surface is covered with the cathode pole piece of nanometer lithium fast-ionic conductor ceramic layer；
B, join solvent is sufficiently mixed according to the mass ratio of 80 ~ 85:5 ~ 10:7 ~ 12 by positive electrode, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, after drying, rolls to obtain anode pole piece；
C, according to different battery core designs, positive pole, cathode pole piece being cut into corresponding size, vacuum drying removes solvent and moisture, standby；
D, positive pole by standby, cathode pole piece, barrier film and electrolyte assemble lithium ion battery, stand 8 ~ 10h；
E, being melted into lithium ion battery, described chemical conversion work step is that 0.01C ~ 0.03C low current charge is charged to 3.8 ~ 4.0V to 3.2 ~ 3.6V, 0.05C ~ 0.1C, is discharged to 2.8 ~ 3.2V with 0.1 ~ 0.3C, and charge and discharge circulates 2 ~ 4 times；
F, the lithium ion battery that has been melted into is stood 5 ~ 9 days, carry out capacity, multiplying power, cycle life test, voltage tester scope 3.0V-4.2V.
The preparation method of described high energy lithium ion cell, wherein, in step A, described nanometer lithium fast-ionic conductor ceramics is Li10GeP2S12、Li3N、La0.5Li0.5TiO3、Li7P3S11、Li10SnPS2、Li11Si2PS12In one.
The preparation method of described high energy lithium ion cell, wherein, in step A, described nanometer lithium fast-ionic conductor ceramic powder particles granularity is 10 ~ 200nm.
The preparation method of described high energy lithium ion cell, wherein, in step A, the nanometer lithium fast-ionic conductor ceramic layer thickness on cathode pole piece surface is 1 10 m.
The preparation method of described high energy lithium ion cell, wherein, in step B, joins positive electrode, conductive agent, binding agent in solvent according to the mass ratio of 82:8:10.
The preparation method of described high energy lithium ion cell, wherein, in step B, described solvent is nmp solvent.
The preparation method of described high energy lithium ion cell, wherein, in step D, described barrier film is Celgard
2400。
The preparation method of described high energy lithium ion cell, wherein, in step D, described electrolyte is LiPF6/EC-EMC-DMC、LiAsF6/PC-EMC-DMC、LiBF4One in/MPC-EMC-DMC.
The preparation method of described high energy lithium ion cell, wherein, in step E, described chemical conversion work step is that 0.02C low current charge is charged to 3.0V to 3.4V, 0.1C.
A kind of high energy lithium ion cell, wherein, uses the preparation method of arbitrary described high energy lithium ion cell to be prepared from.
Beneficial effect: nanometer lithium fast-ionic conductor ceramics is coated, is bonded in metallic lithium surface by the present invention, forms nanometer lithium fast-ionic conductor ceramic layer, it is suppressed that the non-faraday reaction between lithium metal and electrolyte, thus improve the decay resistance of lithium metal；Nanometer lithium fast-ionic conductor ceramic layer decreases the resistance of lithium ion mobility simultaneously, decreases the polarization impedance during battery charge and discharge.
Detailed description of the invention
The present invention provides a kind of high energy lithium ion cell and preparation method thereof, and for making the purpose of the present invention, technical scheme and effect clearer, clear and definite, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
A kind of preparation method of the high energy lithium ion cell of the present invention, wherein, including step:
A, join organic solvent is sufficiently mixed according to 85～90:10～15 mass ratios by nanometer lithium fast-ionic conductor ceramics, bonding agent and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, after drying, roll surface is covered with the cathode pole piece of nanometer lithium fast-ionic conductor ceramic layer；
In described step A, by one layer of nanometer lithium fast-ionic conductor ceramic layer of lithium anode surface-coated so that lithium anode can safe and efficient under conventional electrolysis pendular ring border play a role.Preferably, nanometer lithium fast-ionic conductor ceramics of the present invention can be Li10GeP2S12、Li3N、La0.5Li0.5TiO3、Li7P3S11、Li10SnPS2、Li11Si2PS12In one.
Preferably, described nanometer lithium fast-ionic conductor ceramic powder particles granularity is 10 ~ 200nm.It is highly preferred that described nanometer lithium fast-ionic conductor ceramic powder particles granularity is 20 ~ 50nm.
Preferably, the nanometer lithium fast-ionic conductor ceramic layer thickness on cathode pole piece surface is 1 10 m.It is highly preferred that the nanometer lithium fast-ionic conductor ceramic layer thickness on cathode pole piece surface is 26 m.
B, join solvent is sufficiently mixed according to the mass ratio of 80 ~ 85:5 ~ 10:7 ~ 12 by positive electrode, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, after drying, rolls to obtain anode pole piece；
Preferably, positive electrode, conductive agent, binding agent are joined in solvent according to the mass ratio of 82:8:10.Wherein, described solvent is N-Methyl pyrrolidone (NMP).
C, according to different battery core designs, positive pole, cathode pole piece being cut into corresponding size, vacuum drying removes solvent and moisture, standby；
D, positive pole by standby, cathode pole piece, barrier film and electrolyte assemble lithium ion battery, stand 8 ~ 10h；
Preferably, in step D, described barrier film is Celgard
2400.Described electrolyte is LiPF6/EC-EMC-DMC、LiAsF6/PC-EMC-DMC、LiBF4One in/MPC-EMC-DMC.
E, being melted into lithium ion battery, described chemical conversion work step is that 0.01C ~ 0.03C low current charge is charged to 3.8 ~ 4.0V to 3.2 ~ 3.6V, 0.05C ~ 0.1C, is discharged to 2.8 ~ 3.2V with 0.1 ~ 0.3C, and charge and discharge circulates 2 ~ 4 times；
Preferably, in step E, described chemical conversion work step is that 0.02C low current charge is charged to 3.0V to 3.4V, 0.1C.
F, the lithium ion battery that has been melted into is stood 5 ~ 9 days, carry out capacity, multiplying power, cycle life test, voltage tester scope 3.0V-4.2V.
The present invention is by being coated with one layer of nanometer lithium fast-ionic conductor ceramic layer at metallic lithium surface; not only prevent lithium metal and electrolyte side reaction during discharge and recharge; and inhibit formation and the growth of lithium metal dendrite; reduce the protecting film resistance to lithium ion mobility simultaneously; significantly slow down the protecting film increase to battery impedance; it is thus possible to while ensure that the circulation safe of battery, raising battery; realize high-energy-density output, meet the energy requirement of electric motor car course continuation mileage.
The present invention also provides for a kind of high energy lithium ion cell, wherein, uses the preparation method of arbitrary described high energy lithium ion cell to be prepared from.Lithium ion battery of the present invention not only has high circulating battery safety and battery, has high battery energy density simultaneously, meets the energy requirement of electric motor car course continuation mileage.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
By the nanometer lithium fast-ionic conductor ceramics Li that D50 is 0.1973N, binding agent, according to 90:10 mass ratio, weigh respectively, join to be sufficiently mixed in organic solvent NMP and uniformly become cathode size, and cathode size will be become in inert atmosphere N2In be applied on lithium paper tinsel, evaporation of solvent, after rolling surface is covered with the lithium anode of nanometer lithium fast-ionic conductor ceramic layer；Join nmp solvent is sufficiently mixed according to the mass ratio of 82:8:10 by LiFePO 4 of anode material, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, dry, roll after anode pole piece；According to different battery core designs, positive pole, cathode pole piece are cut into corresponding size, and the present embodiment 1 battery core is designed and sized to 8(T) × 34(W) × 50 (H) mm.120 DEG C of vacuum drying remove solvent and moisture, standby；With Celgard 2400 as barrier film, the LiPF of 1mol/L6/ EC-EMC-DMC(volume ratio is 1:1:1) it is electrolyte, assemble lithium ion battery, stand 8h.
Being melted into battery, described chemical conversion work step is that 0.02C low current charge is charged to 4.0V to 3.4V, 0.08C, is discharged to 3.0V with 0.1C, and charge and discharge circulates 3 times；To the battery standing being melted into 7 days, carry out capacity, multiplying power, cycle life test, voltage tester scope 3.0V-4.2V.
Test result: 5C charge and discharge, battery capacity is 145mAh/g；Circulating 500 times, capability retention is 83%.
Embodiment 2
By the nanometer lithium fast-ionic conductor ceramics Li that D50 is 0.10310GeP2S12, binding agent is according to 85:15 mass ratio, weigh respectively, join organic solvent NMP is sufficiently mixed and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, evaporation of solvent, obtains surface and is covered with the lithium anode of nanometer lithium fast-ionic conductor ceramic layer after rolling；Join nmp solvent is sufficiently mixed according to the mass ratio of 82:8:10 by LiFePO 4 of anode material, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, dry, roll after anode pole piece；According to different battery core designs, positive pole, cathode pole piece are cut into corresponding size, and the present embodiment 2 battery core is designed and sized to 8(T) × 34(W) × 50 (H) mm.120 DEG C of vacuum drying remove solvent and moisture, standby；With Celgard 2400 as barrier film, the LiBF of 1mol/L4/ MPC-EMC-DMC(volume ratio is 1:1:1) it is electrolyte, assemble lithium ion battery, stand 8h.
Test condition is 149mAh/g with embodiment 1, test result: 5C charge and discharge, battery capacity；Circulating 500 times, capability retention is 87%.
Embodiment 3
By the nanometer lithium fast-ionic conductor ceramics La that D50 is 0.050.5Li0.5TiO3, binding agent is according to 90:10 mass ratio, weigh respectively, join nmp solvent is sufficiently mixed and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, evaporation of solvent, obtains surface and is covered with the lithium anode of nanometer lithium fast-ionic conductor ceramic layer after rolling；Join nmp solvent is sufficiently mixed according to the mass ratio of 82:8:10 by LiFePO 4 of anode material, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, dry, roll after anode pole piece；According to different battery core designs, positive pole, cathode pole piece are cut into corresponding size, and the present embodiment 3 battery core is designed and sized to 8(T) × 34(W) × 50 (H) mm.120 DEG C of vacuum drying remove solvent and moisture, standby；With Celgard 2400 as barrier film, the LiBF of 1mol/L4/ EC-EMC-DMC(volume ratio is 1:1:1) it is electrolyte, assemble lithium ion battery, stand 8h.
Test condition with embodiment 1, test result is: 5C charge and discharge, and battery capacity is 146mAh/g；Circulating 500 times, capability retention is 81%.
Embodiment 4
By the nanometer lithium fast-ionic conductor ceramics Li that D50 is 0.027P3S11, binding agent is according to 85:15 mass ratio, weigh respectively, join nmp solvent is sufficiently mixed and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, evaporation of solvent, obtains surface and is covered with the lithium anode of nanometer lithium fast-ionic conductor ceramic layer after rolling；Join nmp solvent is sufficiently mixed according to the mass ratio of 82:8:10 by LiFePO 4 of anode material, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, dry, roll after anode pole piece；According to different battery core designs, positive pole, cathode pole piece are cut into corresponding size, and the present embodiment 4 battery core is designed and sized to 8(T) × 34(W) × 50 (H) mm.120 DEG C of vacuum drying remove solvent and moisture, standby；With Celgard 2400 as barrier film, the LiPF of 1mol/L6/ EC-EMC-DMC(volume ratio is 1:1:1) it is electrolyte, assemble lithium ion battery, stand 8h.
Test condition with embodiment 1, test result is: 5C charge and discharge, and battery capacity is 141mAh/g；Circulating 500 times, capability retention is 82.7%.
Comparative example 1
With metallic lithium foil as negative pole；Join nmp solvent is sufficiently mixed according to the mass ratio of 82:8:10 by positive electrode, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent LiFePO4 is applied on aluminium foil, dry, roll after anode pole piece；According to different battery core designs, positive pole, cathode pole piece are cut into corresponding size, and this comparative example 1 battery core is designed and sized to 8(T) × 34(W) × 50 (H) mm.120 DEG C of vacuum drying remove solvent and moisture, standby；With Celgard 2400 as barrier film, the LiPF of 1mol/L6/ EC-EMC-DMC(volume ratio is 1:1:1) it is electrolyte, assemble lithium ion battery, stand 8h.
Test condition with embodiment 1, test result is: 5C charge and discharge, and battery capacity is 147mAh/g；Circulating 500 times, capability retention is 62.1%.
In sum, a kind of high energy lithium ion cell that the present invention provides and preparation method thereof, the present invention is by being coated with one layer of nanometer lithium fast-ionic conductor ceramic layer at metallic lithium surface, not only prevent lithium metal and electrolyte side reaction during discharge and recharge, and inhibit formation and the growth of lithium metal dendrite, reduce the protecting film resistance to lithium ion mobility simultaneously, significantly slow down the protecting film increase to battery impedance, it is thus possible to ensure that the circulation safe of battery, while improving battery, realize high-energy-density output, meet the energy requirement of electric motor car course continuation mileage.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (10)
1. the preparation method of a high energy lithium ion cell, it is characterised in that include step:
A, join organic solvent is sufficiently mixed according to 85～90:10～15 mass ratios by nanometer lithium fast-ionic conductor ceramics, bonding agent and uniformly become cathode size, cathode size is applied in inert atmosphere on lithium paper tinsel, after drying, roll surface is covered with the cathode pole piece of nanometer lithium fast-ionic conductor ceramic layer；
B, join solvent is sufficiently mixed according to the mass ratio of 80 ~ 85:5 ~ 10:7 ~ 12 by positive electrode, conductive agent, binding agent and uniformly become anode sizing agent, anode sizing agent is applied on aluminium foil, after drying, rolls to obtain anode pole piece；
C, according to different battery core designs, positive pole, cathode pole piece being cut into corresponding size, vacuum drying removes solvent and moisture, standby；
D, positive pole by standby, cathode pole piece, barrier film and electrolyte assemble lithium ion battery, stand 8 ~ 10h；
E, being melted into lithium ion battery, described chemical conversion work step is that 0.01C ~ 0.03C low current charge is charged to 3.8 ~ 4.0V to 3.2 ~ 3.6V, 0.05C ~ 0.1C, is discharged to 2.8 ~ 3.2V with 0.1 ~ 0.3C, and charge and discharge circulates 2 ~ 4 times；
F, the lithium ion battery that has been melted into is stood 5 ~ 9 days, carry out capacity, multiplying power, cycle life test, voltage tester scope 3.0V-4.2V.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step A, described nanometer lithium fast-ionic conductor ceramics is Li10GeP2S12、Li3N、La0.5Li0.5TiO3、Li7P3S11、Li10SnPS2、Li11Si2PS12In one.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step A, described nanometer lithium fast-ionic conductor ceramic powder particles granularity is 10 ~ 200nm.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step A, the nanometer lithium fast-ionic conductor ceramic layer thickness on cathode pole piece surface is 1 10 m.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step B, joins positive electrode, conductive agent, binding agent in solvent according to the mass ratio of 82:8:10.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step B, described solvent is nmp solvent.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step D, described barrier film is Celgard 2400.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step D, described electrolyte is LiPF6/EC-EMC-DMC、LiAsF6/PC-EMC-DMC、LiBF4One in/MPC-EMC-DMC.
The preparation method of high energy lithium ion cell the most according to claim 1, it is characterised in that in step E, described chemical conversion work step is that 0.02C low current charge is charged to 3.0V to 3.4V, 0.1C.
10. a high energy lithium ion cell, it is characterised in that use the preparation method of the high energy lithium ion cell as described in claim 1 ~ 9 is arbitrary to be prepared from.
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