CN103779579A - Lithium battery negative electrode sheet and preparation method thereof as well as lithium battery preparation method - Google Patents
Lithium battery negative electrode sheet and preparation method thereof as well as lithium battery preparation method Download PDFInfo
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- CN103779579A CN103779579A CN201410034906.5A CN201410034906A CN103779579A CN 103779579 A CN103779579 A CN 103779579A CN 201410034906 A CN201410034906 A CN 201410034906A CN 103779579 A CN103779579 A CN 103779579A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 198
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000009713 electroplating Methods 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000004513 sizing Methods 0.000 claims description 30
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 23
- 230000004888 barrier function Effects 0.000 claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 238000003825 pressing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 17
- 230000008859 change Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000012163 sequencing technique Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 230000009977 dual effect Effects 0.000 description 18
- 239000005030 aluminium foil Substances 0.000 description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000006245 Carbon black Super-P Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a lithium battery negative electrode sheet and a preparation method thereof as well as a lithium battery preparation method. The lithium battery negative electrode sheet comprises a negative electrode current collector manufactured by adopting a metal foil or a metal net, a lithium layer arranged on the surface of the negative electrode current collector and a negative electrode tab connected with the negative electrode current collector; a metal lithium layer is plated on the surface of the negative electrode current collector in an electroplating manner, and compared with the conventional lithium battery, the lithium battery disclosed the invention can greatly save the battery space and improve the energy density; the metal lithium layer is plated on the metal foil or the metal net in an electroplating manner, so that the negative electrode lithium layer is thinned and the tensile strength of the lithium layer is improved; compared with the primary lithium battery, the lithium battery achieves heavy current discharge and improves the power density; the difficulty that the primary lithium battery is required to be manufactured in a drying or inert atmosphere is avoided and the manufacture cost of the battery is reduced.
Description
Technical field
The present invention relates to lithium battery processing technique field, relate in particular to a kind of lithium battery cathode plate and preparation method thereof and corresponding lithium battery preparation method.
Background technology
It is wide that lithium battery has operating temperature range, discharging voltage balance, the advantage such as self-discharge rate is low, long service life, the fields such as various fields, particularly space flight and aviation, military affairs, long-life instrument and meter, material flow tracking, automotive electronics, mobile digital product are widely used in.
In recent years, along with scientific and technological development, the function of electronic equipment is constantly upgraded, and lithium ion battery applications scope is more and more wider, therefore the energy density to lithium battery and high rate performance are had higher requirement, and high energy and high power lithium battery have become the primary study direction of lithium battery industry.
The research direction of high energy and power battery is positive and negative pole material, and the disposable lithium-battery take lithium metal as negative pole makes disposable lithium-battery have higher energy density because negative pole lithium metal has high gram volume (3860mAh/g).Conventional disposable lithium-battery, the making of its negative pole metal lithium sheet normally stretches lithium metal piece or lithium ingot mode by extruding or mold pressing is made into the metal lithium bands of certain size; There are two shortcomings and make lithium sheet by extruding or mold pressing: the one, it is in uneven thickness that extruding (mold pressing) stretches, and the consistency of lithium sheet is difficult to guarantee; The 2nd, because the metal strength of lithium is lower, easily broken in the metal lithium bands process that extrusion stretching is thin, the utilance of lithium is low and be difficult to make thin metal lithium bands, and the thinnest lithium band that the mode stretching by extruding or mold pressing at present can realize is about 0.06mm(, and 60 μ are m).Because thin lithium anode is difficult to make, therefore the manufacture method of conventional disposable lithium-battery negative pole is difficult to meet the high power requirement of lithium battery; Because lithium metal has high activity and insecurity, its preparation need to be operated in as nitrogen or argon gas atmosphere at dry or inert atmosphere in addition, the cost of manufacture of lithium anode is improved greatly.
And current business-like lithium ion battery negative material adopts the various embedding lithium material with carbon elements with strong conductivity mostly, the making of its negative plate is by utilizing the mode of film to coat negative active core-shell material on the surface of conductive current collector, the coated surface density of pole piece can be controlled, and therefore can meet the power requirement of electronic equipment.Although lithium metal relatively, material with carbon element is having very large improvement aspect security performance, cycle performance, but still there are many shortcomings: the theoretical gram volume of carbon material negative pole is 372mAh/g, in the time discharging and recharging for the first time, can form passivating film at carbon surface, cause capacitance loss, first charge-discharge efficiency is low; And because the electrode potential of carbon electrode and lithium metal is close, in the time of battery overcharge, still may, at carbon electrodes precipitating metal lithium, cause short circuit and form dendrite; Have an effect with electrolyte and may be in the time of high temperature thermal runaway etc.Therefore the research of high energy and power lithium battery is mainly the energy density that improves the power density of disposable lithium-battery and improve rechargeable lithium ion batteries.High power disposable lithium-battery normally reaches the object of thinning lithium anode by lithium metal is loaded into thin conductive support by the mode of deposition or spraying as (Copper Foil, nickel screen etc.) on wire netting or metal tape to improve its mechanical resistance tensile strength, but the mode of utilizing deposition or spraying makes manufacturing process obviously complicated, be difficult to realize continuous production, and the utilance of lithium metal is low.And the research of high energy lithium ion cell is mainly positive and negative pole material, compared with carbon negative pole, alloy type negative material generally has higher specific capacity, but cycle performance is poor and have problems such as volumetric expansion.
Summary of the invention
One object of the present invention is: a kind of lithium battery cathode plate of energy density and preparation method of this lithium battery cathode plate that can improve the power density of disposable lithium-battery and improve rechargeable lithium ion batteries is provided.
Another object of the present invention is: the preparation method that a kind of lithium battery that comprises above-mentioned lithium battery cathode plate is provided.
For reaching this object, the present invention by the following technical solutions:
On the one hand, provide a kind of lithium battery cathode plate, comprise the negative current collector that adopts metal foil or wire netting to make, be arranged at the lithium layer of described negative pole currect collecting surface and be connected to the negative lug of described negative current collector.
As the preferred technical scheme of one, the upper and lower surface of described negative current collector is arranged alternately fluted, and described lithium layer fills up described groove and covers the upper and lower surface of described negative current collector.
Preferably, described negative current collector is 6～25 μ m by thickness metal foil or wire netting are made.
Preferred, the thickness of described negative current collector is 6～60 μ m, and the upper and lower surface of described negative current collector forms concaveconvex structure or the tortuous structure with alternating groove by roll-in or mold pressing, and the volume of described groove should be less than or equal to 54 μ m
3/ μ m
2.
Preferably, the lithium layer thickness on described negative current collector is 8～80 μ m.Preferred, the lithium layer thickness on described negative current collector is 2～54 μ m.
Negative plate of the present invention, with lithium metal level, compared with conventional lithium ion battery, because the capacity of lithium metal is large more than carbon negative pole material, therefore utilizes negative pole of the present invention can save greatly battery space, has improved the energy density of battery.Negative current collector of the present invention adopts metal foil or wire netting to make, can thinning negative pole lithium layer and increase the tensile strength of lithium by lithium layer is set on this negative current collector, realize the heavy-current discharge of battery, and improve the power density of battery.
What negative current collector arranged concaveconvex structure or tortuous structure can play cushioning effect, provide collector flexible space, increase the useful load of unit are lithium metal, avoid negative current collector because the volumetric expansion of plating lithium causes the fracture of both positive and negative polarity collector, improve the recoverable amount of electrolyte in battery simultaneously.
Preferably, described groove can be square groove, dovetail groove or deep-slotted chip breaker etc.
Described negative current collector is not limited to groove or tortuous structure, and it can also be the laminated structure of surfacing, and described lithium layer is evenly arranged at the upper and lower surface of described negative current collector.
On the other hand, provide a kind of preparation method of lithium battery cathode plate as above, comprise the following steps:
Step S21, provide the negative current collector described in claim 1;
Step S22, at described negative current collector electroplating surface lithium layer;
Step S23, on described negative current collector welding or riveted joint conductive metal band as negative lug;
Described step S22 and described step S23 are without sequencing.
As the preferred technical scheme of one, the mode of electroplating lithium layer described in step S22 is electroless plating or utilizes lithium ion battery to change into principle and electroplate.
As the preferred technical scheme of one, described electroless plating is using negative current collector as negative electrode, and lithium metal, lithium salts or lithium-containing compound are electroplated as anode.
As the preferred technical scheme of one, describedly utilize lithium ion battery to change into principle to electroplate as in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociate to negative pole and electroplate and form described lithium layer in negative pole currect collecting surface.
Simultaneously can thinning negative pole lithium layer and increase the tensile strength of lithium layer by the mode of electroplating on metal forming or wire netting, compared with disposable lithium-battery, the present invention has realized the heavy-current discharge of lithium battery, has improved the power density of battery.
On the one hand, provide a kind of lithium battery preparation method with lithium battery cathode plate as above again, comprise the following steps:
Step S1, making positive plate: the anode sizing agent, the anode collection matrix that include positive electrode active materials are provided, and anode sizing agent is evenly coated on anode collection matrix, obtain being attached with the plus plate current-collecting body of the anodal diaphragm that comprises positive electrode active materials, after being colded pressing, described plus plate current-collecting body cuts, and weld positive pole ear, obtain positive plate;
Step S2, making negative current collector: getting metal foil or the wire netting making thickness that thickness is 6～25 μ m is the negative current collector of 6～60 μ m, and on negative current collector, welds or rivet conductive metal band as negative lug;
Step S3, making barrier film: cut and obtain barrier film according to certain length and width;
Step S4, make electrolyte: lithium salts is joined and in solvent, makes electrolyte;
Step S5, battery assembling: positive plate, barrier film and negative current collector, by stacked or reel and make lithium battery electric core, then packed into battery core after injecting electrolyte in pack case and sealed;
Step S6, lithium battery change into and aging: the lithium battery to step S5 charges, and in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociating to negative pole and electroplating forms described lithium layer in negative pole currect collecting surface, then lithium battery is carried out to aging moulding.
As the preferred technical scheme of one, in described step S1, described anode sizing agent for stirring positive electrode active materials and polyvinylidene fluoride binding agent and conductive carbon to make in 1-METHYLPYRROLIDONE solvent.
Preferably, the acid of the cobalt take gram volume as 140mAh/g lithium (LiCoO
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 95:2:3, make anode sizing agent, by 33.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.107mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm.
Preferably, the nickle cobalt lithium manganate (LiNi take gram volume as 146mAh/g
0.4co
0.2mn
0.4o
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 94.5:2:3.5, make anode sizing agent, by 30.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.107mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm.
Preferably, the LiMn2O4 (LiMnO take gram volume as 100mAh/g
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 94.5:2:3.5, make anode sizing agent, by 27.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.102mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm.
As the preferred technical scheme of one, in described step S2, the upper and lower surface of described negative current collector forms concaveconvex structure or the tortuous structure with alternating groove by roll-in or mold pressing, and the volume of described groove should be less than or equal to 54 μ m
3/ μ m
2.
As the preferred technical scheme of one, in described step S6, to the aging flow process of changing into of lithium battery be 0.05～0.2C current charges to after 4.0V with 0.2～1C current charges to 4.2～4.5V, and in 40～50 ℃ of environment aging 24～72h.
Beneficial effect of the present invention is: surface density and size that lithium metal on negative current collector is electroplated in the capacity requirement control that the prepared negative pole of the present invention can be set according to battery, and realize uniformity and the consistency of plated metallic lithium on negative current collector according to the size of electroplating current, improve the security performance of battery.
Mode lithium metal layer on negative current collector plated surface that negative pole utilization is electroplated, compared with conventional lithium ion battery, save greatly battery space, improve the energy density of battery, and simultaneously can thinning negative pole lithium layer and increase the tensile strength of lithium layer by the mode of electroplating on metal forming or wire netting, compared with disposable lithium-battery, the present invention has realized the heavy-current discharge of lithium battery, improve the power density of battery, and the difficult point of having avoided disposable lithium-battery to make in dry or inert atmosphere, has reduced the cost of manufacture of battery.
Accompanying drawing explanation
According to drawings and embodiments the present invention is described in further detail below.
Fig. 1 is negative current collector schematic cross-section described in the embodiment of the present invention 1.
Fig. 2 is negative plate schematic cross-section described in the embodiment of the present invention 1.
Fig. 3 is negative plate floor map described in the embodiment of the present invention 1.
Fig. 4 is negative current collector schematic cross-section described in the embodiment of the present invention 2,3.
Fig. 5 is negative plate schematic cross-section described in the embodiment of the present invention 2,3.
In Fig. 1 to 3:
11, negative current collector; 12, lithium layer; 13, negative lug.
In Fig. 4,5:
21, negative current collector; 22, lithium layer; 23, negative lug.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by embodiment.
Embodiment 1:
As shown in Figures 1 to 3, a kind of lithium battery cathode plate described in the present embodiment, comprise adopt metal foil make negative current collector 11, by electroplate mode be arranged at the lithium layer 12 on negative current collector 11 surfaces and be connected to the negative lug 13 of negative current collector 11; The laminated structure that negative current collector 11 is surfacing, lithium layer 12 is evenly arranged at the upper and lower surface of negative current collector 11.
Described in the present embodiment, lithium battery cathode plate adopts following methods to be prepared from:
Step S21, provide negative current collector as above, in one end of negative current collector welding negative lug;
Step S22, utilize lithium ion battery to change into principle at described negative current collector electroplating surface lithium layer, utilizing lithium ion battery to change into principle electroplates as in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociate to negative pole and electroplate and form described lithium layer in negative pole currect collecting surface.
Described in the present embodiment, lithium battery adopts following methods to be prepared from:
S1, making positive plate: the cobalt acid lithium (LiCoO take gram volume as 140mAh/g
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 95:2:3, make anode sizing agent, by 33.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.107mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm;
S2, make negative current collector: it is the Copper Foil that 153mm, width are 44mm that the Copper Foil of getting 9 μ m cuts into length, and on collector, welds negative lug, obtains negative current collector, and structure as shown in Figure 1;
S3, making barrier film: adopting thickness is three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) of 16 μ m, and length is that 320mm, width are 46mm;
The making of S4, electrolyte: by lithium hexafluoro phosphate (LiPF
6) join in solvent, mix and obtain electrolyte, wherein, described solvent is the mixed liquor of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC);
The making of S5, lithium battery: positive plate obtained above, barrier film and negative current collector are reeled and obtained lithium battery electric core, then battery core is packed in aluminum plastic film pack case and after injecting electrolyte and sealed;
S6, lithium battery change into and aging: with 13mA(0.05C) the electric current lithium cell charging that just step (5) makes to 4.0V, use again 52mA(0.2C) current charges to 4.2V, then lithium battery aging 48h aftershaping in 45 ℃ of baking boxs is obtained to the embodiment of the present invention 1 negative pole and contains the lithium battery that negative pole model of the present invention is 68500, the thickness of wherein electroplating lithium layer on negative current collector is 20 μ m, and its sectional view and plane graph are respectively as shown in Figures 2 and 3.
Comparative example 1:
Described in this comparative example, lithium battery adopts following methods to be prepared from:
(1) making of positive plate: the cobalt acid lithium (LiCoO take gram volume as 140mAh/g
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 95:2:3, make anode sizing agent, by 28.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 120mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 82mm and 100mm, cutting into width through colding pressing is that 42mm, thickness are 0.093mm pole piece, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm;
(2) making of negative plate: the graphite take gram volume as 350mAh/g is negative active core-shell material, with binding agent butadiene-styrene rubber (SBR), thickener carboxymethyl cellulose (CMC) and conductive agent Super-P press mass ratio mixing and stirring in deionized water of 95:1.8:1.5:1.7, make cathode size, the size that is 100mm take the density of 12.4mg/cm2 by dual coating length is 9 μ m by cathode size dual coating at thickness, length is on the Copper Foil of 105mm, cutting into width through colding pressing is 44mm, thickness is the pole piece of 0.09mm, and weld negative lug and obtain surface attachment and have the negative plate of cathode membrane,
(3) making of barrier film: adopting thickness is three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) of 16 μ m, and length is that 265mm, width are 46mm;
(4) making of electrolyte: by lithium hexafluoro phosphate (LiPF
6) join in solvent, mix and obtain electrolyte, wherein, described solvent is the mixed liquor of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC);
(5) making of lithium battery: positive plate obtained above, barrier film and negative plate are reeled and obtained lithium battery electric core, then battery core is packed in aluminum plastic film pack case and after injecting electrolyte and sealed;
(6) lithium battery change into and aging: with 13mA(0.1C) electric current lithium cell charging that step (5) is made to 4.0V, then use 52mA(0.4C) current charges to 4.2V, moulding obtains the lithium battery that comparative example 1 model is 68500.
Comparative example 2:
Described in this comparative example, lithium battery adopts following methods to be prepared from:
(1) making of positive plate: the manganese dioxide (MnO take gram volume as 270mAh/g
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P and KS-6 press 90:3:3.5:3.5, make anode sizing agent, by 28.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 120mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 82mm and 100mm, cutting into width through colding pressing is the pole piece that 44mm, thickness are 0.108mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm;
(2) making of negative plate: getting width and be lithium band that 42mm, thickness are 0.07mm, to cut into length be 95mm lithium sheet, and on lithium sheet punching press negative lug, obtain negative plate;
(3) making of barrier film: adopting thickness is three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) of 16 μ m, and length is 230mm, and width is 46mm;
(4) making of electrolyte: by lithium hexafluoro phosphate (LiPF
6) join in solvent, mix and obtain electrolyte, wherein, described solvent is the mixed liquor of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC);
(5) making of lithium battery: positive plate obtained above, barrier film and negative plate are reeled and obtained lithium battery electric core, then battery core is packed in aluminum plastic film pack case and after injecting electrolyte and sealed;
(6) lithium battery change into and aging: with 13mA(0.05C) the electric current lithium battery that just step (5) makes electric discharge 12min(capacity 1%), then lithium battery aging 48h aftershaping in 45 ℃ of baking boxs is obtained to the lithium battery that comparative example 2 models are 68500.
The lithium battery that above-described embodiment 1, comparative example 1 and comparative example 2 are prepared carries out respectively 100mA and 1000mA electric discharge, and its discharge capacity, platform voltage and self-discharge rate are as shown in table 1:
Table 1
Can be found out by table 1 data, with the lithium ion battery of comparative example 1 and the contrast of the disposable lithium-battery of comparative example 2, utilize the prepared lithium battery of negative pole of the present invention, combine the high-power feature of disposable lithium-battery high-energy and lithium ion battery, energy density and the power density of battery are greatly improved, and have extremely low self-discharge rate, the lithium ion battery that can be used as primary cell or low circulation requirement uses.
Embodiment 2:
As shown in Figure 4,5, a kind of lithium battery cathode plate described in the present embodiment, comprise adopt metal foil make negative current collector 21, by electroplate mode be arranged at the lithium layer 22 on negative current collector 21 surfaces and be connected to the negative lug 23 of negative current collector 21; The upper and lower surface of negative current collector 21 has concaveconvex structure, and lithium layer 22 fills up the groove of concaveconvex structure formation and covers the upper and lower surface of negative current collector 21.
Described in the present embodiment, lithium battery cathode plate adopts following methods to be prepared from:
Step S21, provide negative current collector as above, in one end of negative current collector welding negative lug;
Step S22, utilize lithium ion battery to change into principle at described negative current collector electroplating surface lithium layer, utilizing lithium ion battery to change into principle electroplates as in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociate to negative pole and electroplate and form described lithium layer in negative pole currect collecting surface.
Described in the present embodiment, lithium battery adopts following methods to be prepared from:
The making of S1, positive plate: the nickle cobalt lithium manganate (LiNi take gram volume as 146mAh/g
0.4co
0.2mn
0.4o
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 94.5:2:3.5, make anode sizing agent, by 30.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.107mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm;
The making of S2, negative current collector: it is the tinfoil paper that 153mm, width are 44mm that the tinfoil paper of getting 9 μ m cuts into length, forming thickness by roll-in or mold pressing is 25 μ m the negative current collector with concaveconvex structure, the volume of its concaveconvex structure is 25 μ m3/ μ m2, and on collector, weld negative lug, obtain negative current collector, structure as shown in Figure 4;
The making of S3, barrier film: adopting thickness is three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) of 16 μ m, and length is that 320mm, width are 46mm;
The making of S4, electrolyte: by lithium hexafluoro phosphate (LiPF
6) join in solvent, mix and obtain electrolyte, wherein, described solvent is the mixed liquor of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC);
The making of S5, lithium battery: positive plate obtained above, barrier film and negative current collector are reeled and obtained lithium battery electric core, then battery core is packed in aluminum plastic film pack case and after injecting electrolyte and sealed;
S6, lithium battery change into and aging: with 50mA(0.2C) the electric current lithium cell charging that just step (5) makes to 4.0V, use again 250mA(1C) current charges to 4.3V, then lithium battery aging 36h aftershaping in 50 ℃ of baking boxs is obtained to the embodiment of the present invention 2 negative poles and contains the lithium battery that negative pole model of the present invention is 68500, the thickness of wherein electroplating lithium layer on negative current collector is 19 μ m, and its sectional view as shown in Figure 5.
Embodiment 3:
As shown in Figure 4,5, a kind of lithium battery cathode plate described in the present embodiment, comprise adopt metal foil make negative current collector 21, by electroplate mode be arranged at the lithium layer 22 on negative current collector 21 surfaces and be connected to the negative lug 23 of negative current collector 21; Negative current collector 21 is the laminated structure that upper and lower surface has concaveconvex structure, and lithium layer fills up the groove of concaveconvex structure formation and covers the upper and lower surface of negative current collector 21.
Described in the present embodiment, lithium battery cathode plate adopts following methods to be prepared from:
Step S21, provide negative current collector as above;
Step S22, utilize lithium ion battery to change into principle at described negative current collector electroplating surface lithium layer, utilizing lithium ion battery to change into principle electroplates as in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociate to negative pole and electroplate and form described lithium layer in negative pole currect collecting surface.
(1) making of positive plate: the LiMn2O4 (LiMnO take gram volume as 100mAh/g
2) be positive electrode active materials, with mass ratio mixing and stirring in NMP that binding agent PVDF and conductive agent Super-P press 94.5:2:3.5, make anode sizing agent, by 27.0mg/cm
2density be on 16 μ m, the length aluminium foil that is 168mm by anode sizing agent dual coating at thickness, described anode sizing agent length of dual coating on aluminium foil is respectively 130mm and 152mm, cutting into width through colding pressing is the pole piece that 42mm, thickness are 0.102mm, and welds positive pole ear and obtain surface attachment and have the positive plate of anodal diaphragm;
(2) making of negative current collector: it is the aluminium net that 153mm, width are 44mm that the aluminium net of getting 16 μ m cuts into length, forming thickness by roll-in or mold pressing is 50 μ m the negative current collector with concaveconvex structure, the volume of its concaveconvex structure is 50 μ m3/ μ m2, and on collector, weld negative lug, obtain negative current collector, structure as shown in Figure 4;
(3) making of barrier film: adopting thickness is three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) of 16 μ m, and length is that 320mm, width are 46mm;
(4) making of electrolyte: by lithium hexafluoro phosphate (LiPF
6) join in solvent, mix and obtain electrolyte, wherein, described solvent is the mixed liquor of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC);
(5) making of lithium battery: positive plate obtained above, barrier film and negative current collector are reeled and obtained lithium battery electric core, then battery core is packed in aluminum plastic film pack case and after injecting electrolyte and sealed;
(6) lithium battery change into and aging: with 15mA(0.1C) the electric current lithium cell charging that just step (5) makes to 4.0V, use again 75mA(0.5C) current charges to 4.5V, then lithium battery aging 72h aftershaping in 40 ℃ of baking boxs is obtained to the embodiment of the present invention 3 negative poles and contains the lithium battery that negative pole model of the present invention is 68500, the thickness of wherein electroplating lithium layer on negative current collector is 12 μ m, and its sectional view as shown in Figure 5.
The lithium battery that above-described embodiment 1-3 is prepared carries out respectively 100mA and 1000mA electric discharge, and its discharge capacity, platform voltage and self-discharge rate are as shown in table 2:
Table 2
Can find out that by table 2 data the lithium battery that adopts technical solution of the present invention to prepare has higher power of battery density with respect to existing disposable lithium-battery, and there is higher energy content of battery density with respect to existing lithium ion battery.
What need statement is; above-mentioned embodiment is only preferred embodiment of the present invention and institute's application technology principle; in technical scope disclosed in this invention, the variation that any those skilled in the art of being familiar with easily expect or replacement, all should be encompassed in protection scope of the present invention.
Claims (10)
1. a lithium battery cathode plate, is characterized in that, comprises the negative current collector that adopts metal foil or wire netting to make, is arranged at the lithium layer of described negative pole currect collecting surface and is connected to the negative lug of described negative current collector.
2. lithium battery cathode plate according to claim 1, is characterized in that, the upper and lower surface of described negative current collector is arranged alternately fluted, and described lithium layer fills up described groove and covers the upper and lower surface of described negative current collector.
3. a preparation method for lithium battery cathode plate as claimed in claim 1, is characterized in that, comprises the following steps:
Step S21, provide negative current collector as claimed in claim 1;
Step S22, at described negative current collector electroplating surface lithium layer;
Step S23, on described negative current collector welding or riveted joint conductive metal band as negative lug;
Described step S22 and described step S23 are without sequencing.
4. the preparation method of lithium battery cathode plate according to claim 3, is characterized in that, the mode of electroplating lithium layer described in step S22 is electroless plating or utilizes lithium ion battery to change into principle and electroplate.
5. the preparation method of lithium battery cathode plate according to claim 4, is characterized in that, described electroless plating is using negative current collector as negative electrode, and lithium metal, lithium salts or lithium-containing compound are electroplated as anode.
6. the preparation method of lithium battery cathode plate according to claim 4, it is characterized in that, describedly utilize lithium ion battery to change into principle to electroplate as in charging process, lithium reversible in positive electrode active materials is deviate from, form de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociate to negative pole and electroplate and form described lithium layer in negative pole currect collecting surface.
7. a lithium battery preparation method with lithium battery cathode plate claimed in claim 1, is characterized in that, comprises the following steps:
Step S1, making positive plate: the anode sizing agent, the anode collection matrix that include positive electrode active materials are provided, and anode sizing agent is evenly coated on anode collection matrix, obtain being attached with the plus plate current-collecting body of the anodal diaphragm that comprises positive electrode active materials, after being colded pressing, described plus plate current-collecting body cuts, and weld positive pole ear, obtain positive plate;
Step S2, making negative current collector: getting metal foil or the wire netting making thickness that thickness is 6～25 μ m is the negative current collector of 6～60 μ m, and on negative current collector, welds or rivet conductive metal band as negative lug;
Step S3, making barrier film: cut and obtain barrier film according to certain length and width;
Step S4, make electrolyte: lithium salts is joined and in solvent, makes electrolyte;
Step S5, battery assembling: positive plate, barrier film and negative current collector, by stacked or reel and make lithium battery electric core, then packed into battery core after injecting electrolyte in pack case and sealed;
Step S6, lithium battery change into and aging: the lithium battery to step S5 charges, and in charging process, lithium reversible in positive electrode active materials is deviate from, and forms de-lithium state positive electrode active materials, the Li deviating from from positive pole
+dissociating to negative pole and electroplating forms described lithium layer in negative pole currect collecting surface, then lithium battery is carried out to aging moulding.
8. lithium battery preparation method according to claim 7, is characterized in that, in described step S1, described anode sizing agent for stirring positive electrode active materials and polyvinylidene fluoride binding agent and conductive carbon to make in 1-METHYLPYRROLIDONE solvent.
9. lithium battery preparation method according to claim 7, it is characterized in that, in described step S2, the upper and lower surface of described negative current collector forms concaveconvex structure or the tortuous structure with alternating groove by roll-in or mold pressing, and the volume of described groove should be less than or equal to 54 μ m
3/ μ m
2.
10. lithium battery preparation method according to claim 7, it is characterized in that, in described step S6, to the aging flow process of changing into of lithium battery be 0.05～0.2C current charges to after 4.0V with 0.2～1C current charges to 4.2～4.5V, and in 40～50 ℃ of environment aging 24～72h.
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| CN113328062A (en) * | 2021-05-27 | 2021-08-31 | 贵州梅岭电源有限公司 | High-power-density lithium primary battery negative plate and preparation method thereof |
| CN114639800A (en) * | 2022-02-15 | 2022-06-17 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
| WO2024000784A1 (en) * | 2022-07-01 | 2024-01-04 | 惠州亿纬锂能股份有限公司 | Negative electrode plate and lithium-metal battery |
| EP4325597A4 (en) * | 2022-07-01 | 2025-08-06 | Eve Energy Co Ltd | NEGATIVE ELECTRODE PLATE AND LITHIUM METAL BATTERY |
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