CN107799721A - Prelithiation negative pole including its secondary cell and their manufacture method - Google Patents

Prelithiation negative pole including its secondary cell and their manufacture method Download PDF

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Publication number
CN107799721A
CN107799721A CN201610808809.6A CN201610808809A CN107799721A CN 107799721 A CN107799721 A CN 107799721A CN 201610808809 A CN201610808809 A CN 201610808809A CN 107799721 A CN107799721 A CN 107799721A
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electrode active
negative electrode
negative pole
cushion
lithium metal
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CN107799721B (en
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黄杰
王怡
陆浩
刘柏男
李文俊
李泓
陈立泉
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Beijing WeLion New Energy Technology Co ltd
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Beijing WeLion New Energy Technology Co ltd
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to prelithiation negative pole including its secondary cell and their manufacture method.A kind of manufacture method of prelithiation negative pole for secondary cell may include：The first negative electrode active layer and the first reaction cushion are sequentially formed on the first surface of collector；The first layer containing lithium metal is set to obtain quasi- negative pole structure on the described first reaction cushion；And by the quasi- negative pole structure leaching in the electrolytic solution, make electrochemical reaction occurs between first layer containing lithium metal and the first negative electrode active layer, so as to which the lithium in first layer containing lithium metal is embedded into the first negative electrode active layer to form prelithiation negative pole.

Description

Prelithiation negative pole including its secondary cell and their manufacture method
Technical field
Present invention relates in general to new energy field, more specifically it relates to a kind of prelithiation negative pole for secondary cell, Manufacture the method for the prelithiation negative pole including the secondary cell of the prelithiation negative pole and the method for manufacturing the secondary cell.
Background technology
In recent years, fast-developing electric automobile and energy storage industry are to using lithium ion battery, sodium-ion battery as representative Energy density, cost, cyclicity and the security of secondary cell propose higher requirement.It is conventional by taking lithium ion battery as an example Lithium ion battery mainly use graphite cathode, the theoretical capacity 372mAh/g of graphite cathode, at present domestic main graphite bear Pole manufacturer has been realized in 365mAh/g capacity such as Jiangxi purple great mansion, Shenzhen Bei Terui, close to the pole of theoretical capacity Limit.In order to realize higher energy density and power density, people begin to focus on novel anode material, such as non-graphitized carbon materials Material, oxide material and composite.However, such material is present, irreversible capacity is high, coulombic efficiency is low etc. first seriously asks Topic, easily causes capacity of lithium ion battery to be decreased obviously.At present, in order to solve lithium ion battery negative material coulombic efficiency first The problem of low, researcher propose chemical reduction method, artificial SEI (Solid Electrolyte Interface, solid electricity Solve matter interface) embrane method and electrochemistry prelithiation method etc., wherein electrochemistry prelithiation method is a kind of most direct solution lithium-ion electric The method of the low problem of coulombic efficiency first of pond negative material.
In Chinese patent application the 200480021793.Xth, disclose one kind and directly connect lithium powder with electrode material Touch, then realize the prelithiation method of electrode material by galvanic interaction again.However, this method easily produces " dead lithium ", instead Should be violent, cause the structure of electrode material to be destroyed, and be difficult to form fine and close and stable SEI films, finally cause electrode The cycle performance of material declines.In addition, lithium powder is a kind of more dangerous material, easily burning, therefore the prelithiation of this method Process conditions are more harsh.
In Chinese patent application the 201210573270.2nd, for lithiumation electric current it is big the problem of, disclose a kind of low Warm electrolyte filling method, galvanic interaction is carried out at a lower temperature, control the embedding lithium speed of material, so as to improve the head of material While secondary coulombic efficiency and capacity, improve the cycle performance of material.However, this method needs low-temperature operation, technique is more complicated, Cost is high, and the electrolysis fluid viscosity increase under low temperature, fluid injection operating difficulties.
In Chinese patent application the 201410839836.0th, it is coating lithium metal in positive pole and negative pole, is applied on surface Solid electrolyte is covered, to reduce reaction speed, but complex manufacturing technology, it is not easy large-scale industrial production.
Lithium anode is considered as forth generation negative pole, has and reaches as high as 3860mAh/g capacity and relatively low deposition Current potential (- 3.04V).Battery energy density can be brought up to 300wh/kg by doing negative pole using lithium metal, but the effect of lithium metal Rate, Li dendrite problem are not yet completely resolved.
At present, prelithiation negative pole and lithium metal composite negative pole are considered as a kind of transition negative pole, it is possible to increase lithium metal Efficiency and battery security.
The content of the invention
One aspect of the present invention is to provide a kind of method for manufacturing the prelithiation negative pole for secondary cell, its technique Simply, cost is cheap, and can efficiently control lithiumation speed.
Another aspect of the present invention, which also resides in, provides a kind of prelithiation negative pole for secondary cell, and it has the head improved Secondary coulombic efficiency, dead lithium therein is reduce or eliminated, and with the cycle performance significantly improved.
Another aspect of the present invention also provides a kind of secondary cell, and it includes manufactured prelithiation according to the method described above and born Pole.
According to an exemplary embodiment, a kind of manufacture method of prelithiation negative pole for secondary cell may include：Collecting The first negative electrode active layer and the first reaction cushion are sequentially formed on the first surface of fluid；On the described first reaction cushion The first layer containing lithium metal is set to obtain quasi- negative pole structure；And by the quasi- negative pole structure leaching in the electrolytic solution, make described the Electrochemical reaction occurs between one layer containing lithium metal and the first negative electrode active layer, so as in first layer containing lithium metal Lithium is embedded into the first negative electrode active layer to form prelithiation negative pole.
In some instances, before by the quasi- negative pole structure leaching in the electrolytic solution, methods described is also included by described in Quasi- negative pole structure is assembled into secondary cell together with positive pole, barrier film, wherein the barrier film be arranged on the quasi- negative pole structure with Between the positive pole.
In some instances, before the quasi- negative pole structure is assembled into secondary cell together with positive pole, barrier film, institute Stating method also includes：The second negative electrode active is sequentially formed on the second surface opposite with the first surface of the collector Layer and the second reaction cushion；And
The second layer containing lithium metal is set on the described second reaction cushion,
Wherein, when by the quasi- negative pole structure leaching in the electrolytic solution, second layer containing lithium metal and described second negative Electrochemical reaction occurs between the active layer of pole, so as to which the lithium in second layer containing lithium metal is embedded into second negative electrode active In layer.
In some instances, the quasi- negative pole structure leaching is included in the electrolytic solution：Electricity is injected into the secondary cell Liquid is solved to infiltrate the quasi- negative pole structure；And the secondary cell for being injected with electrolyte is stood into the scheduled time to complete Electrochemical reaction is stated, so as to obtain the prelithiation negative pole.
In some instances, each being led including electronics in the first reaction cushion and the second reaction cushion At least one of body material and electron-ion mixed conductor material and polymer.
In some instances, the electron conductor material includes carbon black, Ke Qin carbon, acetylene black, Super P, graphene, list Wall or multi-walled carbon nanotube, copper powder, aluminium powder, native graphite, Delanium, soft carbon, hard carbon, siliceous, tin, germanium, zinc, aluminium, boron, magnesium Material, molybdenum dioxide and their any combination of element.
In some instances, the electron-ion mixed conductor material native graphite, Delanium, soft carbon, hard carbon, silicon, Germanium, lithium titanate, titanium dioxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, tin oxide, stannous oxide, the sub- silicon of oxidation, vulcanization Iron, ferrous sulfide, Li3xLa2/3-xTiO3、LiZr2-yTiy(PO4)3、Li1+zAlzTi2-z(PO4)3And their any combination, Wherein 0≤x≤2/3,0≤y≤2,0≤z≤2.
In some instances, the polymer includes Vingon (PVDF), Vingon-hexafluoropropene (PVDF- HFP), polytetrafluoroethylene (PTFE) (PTFE), polyethylene glycol oxide, polyester, polyamide, polyamidoimide, polymethyl methacrylate, poly- Carbonic ester, carboxymethyl cellulose, SB, polyacrylic acid, Lithium polyacrylate, polyacrylonitrile, carboxymethyl are fine Tie up plain sodium, butadiene-styrene rubber and their any combination.
In some instances, the mass percent shared by the polymer is 30%~99.99%, the electronic conductor material Mass percent shared by material and the electron-ion mixed conductor material is 0.01%~70%.
In some instances, each metal is included in first layer containing lithium metal and second layer containing lithium metal Lithium, Li-Si alloy, lithium-aluminium alloy, lithium boron alloy, lithium magnesium alloy and their any combination.
In some instances, the concentration of the electrolyte can be in 0.01mol/L~3mol/L scope.
In some instances, each thickness in the first reaction cushion and the second reaction cushion exists 0.05 μm to 40 μm of scope.
In some instances, it is described first reaction cushion and it is described second reaction cushion in be each pantostrat or Discontinuity layer.
In some instances, it is described first reaction cushion and it is described second reaction cushion in be each it is porous or Fine and close.
In some instances, each thickness in first layer containing lithium metal and second layer containing lithium metal exists 10nm-80 μm of scope.
In some instances, first layer containing lithium metal and second layer containing lithium metal respectively can be partially or completely The ground covering first reaction cushion and the second reaction cushion.
In some instances, in first layer containing lithium metal and second layer containing lithium metal be each pantostrat or Person has through hole to expose the first reaction cushion and the second reaction cushion under it.
According to another exemplary embodiment, a kind of prelithiation negative pole for secondary cell may include：Collector；It is arranged on The first negative electrode active layer on the first surface of the collector；And first be arranged on the first negative electrode active layer is anti- Cushion is answered, wherein, the first negative electrode active layer is through the first reaction cushion lithiumation.
In some instances, the prelithiation negative pole also includes：It is being arranged on the collector with the first surface phase The second negative electrode active layer on anti-second surface；And it is arranged on the second reaction buffering on the second negative electrode active layer Layer, wherein, the second negative electrode active layer is through the second reaction cushion lithiumation.
According to another exemplary embodiment, a kind of method for manufacturing secondary cell may include：In the first surface of collector On sequentially form the first negative electrode active layer and first reaction cushion；First is set on the described first reaction cushion containing lithium gold Belong to layer to obtain quasi- negative pole structure；The quasi- negative pole structure is assembled into secondary cell together with positive pole, barrier film, wherein described Barrier film is arranged between the quasi- negative pole structure and the positive pole；And electrolyte is injected into the secondary cell, make described Electrochemical reaction occurs between first layer containing lithium metal and the first negative electrode active layer, so as in first layer containing lithium metal Lithium be embedded into the first negative electrode active layer to form prelithiation negative pole.
In some instances, before the quasi- negative pole structure is assembled into secondary cell together with positive pole, barrier film, institute Stating method also includes：The second negative electrode active is sequentially formed on the second surface opposite with the first surface of the collector Layer and the second reaction cushion；And the second layer containing lithium metal is set on the described second reaction cushion.
According to another exemplary embodiment, a kind of secondary cell may include：Housing；And it is arranged in the housing just Pole, barrier film and prelithiation negative pole, the barrier film is between the positive pole and the prelithiation negative pole, the prelithiation negative pole bag Include：Collector；The first negative electrode active layer being arranged on the first surface of the collector；And it is arranged on first negative pole The first reaction cushion on active layer, wherein, the first negative electrode active layer is through the first reaction cushion lithiumation.
In some instances, the prelithiation negative pole also includes：It is being arranged on the collector with the first surface phase The second negative electrode active layer on anti-second surface；And it is arranged on the second reaction buffering on the second negative electrode active layer Layer, wherein, the second negative electrode active layer is through the second reaction cushion lithiumation.
In certain embodiments, the barrier film may include：Polymer film；And at least one coated in the polymer film Conductive particles layer on individual surface.
In certain embodiments, the conductive particle layer may include ion conductor particle, electron conductor particles, ion-electricity Sub- mixed conductor particle or their any combination.
Brief description of the drawings
Shown in the drawings of the exemplary embodiment of the present invention.It should be understood that what accompanying drawing was not drawn to scale.
Figure 1A to 1E shows according to an embodiment of the invention manufacture for the prelithiation negative pole of secondary cell and secondary Each interstage of the method for battery；
Fig. 2 shows the prelithiation negative pole and secondary cell according to another embodiment of the present invention manufactured for secondary cell Method an interstage；
Fig. 3 shows that the relation that the voltage of the secondary cell according to one embodiment of the invention and comparative example changes over time is bent Line；
Fig. 4 shows the surface scan electromicroscopic photograph of the prelithiation negative pole prepared according to one embodiment of the invention；
Fig. 5 A show the cyclic curve of the secondary cell of a comparative example；And
Fig. 5 B show the circulating battery curve of the example of secondary cell according to an embodiment of the invention.
Embodiment
With reference to the accompanying drawings come describe the present invention exemplary embodiment.
Figure 1A to 1E shows according to an embodiment of the invention manufacture for the prelithiation negative pole of secondary cell and secondary Each interstage of the method for battery.As shown in Figure 1A, this method includes forming negative electrode active layer on the current collector 110 first 120.In certain embodiments, collector 110 may include that copper foil, nickel foil, stainless steel foil, iron foil, carbon film, graphene film, carbon are received Mitron film, carbon-fiber film and their composite membrane etc..Collector 110 can also have through its multiple through holes.In some realities Apply in example, the thickness of collector 110 can be in such as 1-50 μm of scope.In order to increase collector and negative active core-shell material it Between caking property and electric conductivity, 0.1-2 μm of carbon-coating can be coated in collection liquid surface.
Negative electrode active layer 120 includes the negative active core-shell material for reversibly storing lithium.In certain embodiments, reversibly Store lithium negative active core-shell material example include but is not limited to for example native graphite, Delanium, soft carbon, hard carbon, it is siliceous, Tin, germanium, zinc, aluminium, boron, the material of magnesium elements, transition metal oxide, transient metal sulfide, transition metal fluorides, transition Metal nitride, transition metal phosphide, wherein the transition metal can be selected from Cr, Cu, Fe, Co, Ni, Nb, V, Mo, W and Ru.Negative electrode active layer 120 may also include electronic conductive additive material and adhesive material, wherein electronic conductive additive material Example include but is not limited to carbon black, acetylene black, CNT, carbon fiber, graphene, graphene oxide and they appoint Meaning combination.The example of adhesive material includes but is not limited to Vingon (PVDF), Vingon-hexafluoropropene (PVDF- HFP), polytetrafluoroethylene (PTFE) (PTFE), polyethylene glycol oxide, polyester, polyamide, polyamidoimide, polymethyl methacrylate, poly- Carbonic ester, carboxymethyl cellulose, SB, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-styrene rubber and Their any combination.In certain embodiments, the electronic conductive additive material in negative electrode active layer 120 accounts for negative electrode active layer The percentage of 120 gross mass can be 0.5-10%；Adhesive material in negative electrode active layer 120 accounts for negative electrode active layer 120 The percentage of gross mass can be 0.5-10%.
In certain embodiments, solvent (for example, water) can be utilized negative active core-shell material, electronic conductive additive, glued Agent is connect to be stirred, then by mixture coating on the current collector 110, drying, so as to prepare negative electrode active layer 120.Negative pole The thickness of active layer 120 can be such as 2-200 μm.
Although in the embodiment shown in Figure 1A, negative electrode active layer 120 is shown as covering the whole surface of collector 110, It is it should be understood that the invention is not restricted to this.In further embodiments, negative electrode active layer 120 can also only cover collector 110 A part.In certain embodiments, collector 110 not may be electrically connected to by the part that negative electrode active layer 120 covers it is secondary The miscellaneous part of battery, such as negative terminal.
Next, as shown in Figure 1B, reaction cushion 130 can be formed on negative electrode active layer 120.As below by detail As description, reaction cushion 130 can delay the speed of the lithiation of negative electrode active layer 120, many have so as to obtain Beneficial effect.The step of forming reaction cushion 130 may particularly include following steps.
First, the slurry for forming reaction cushion 130 is prepared.Specifically, polymer and solvent can be mixed Stirring, make polymer uniform scattered in a solvent.Example available for the polymer of reaction cushion 130 includes but is not limited to poly- It is vinylidene chloride (PVDF), Vingon-hexafluoropropene (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE), polyethylene glycol oxide, poly- Ester, polyamide, polyamidoimide, polymethyl methacrylate, makrolon, carboxymethyl cellulose, styrene-butadiene are common Polymers, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-styrene rubber and their any combination.Reaction cushion 130 includes Solvent can be such as organic solvent, and its example may include but be not limited to 1-METHYLPYRROLIDONE, acetonitrile, acetone, N, N- diformazans Base formamide, ethanol and their any combination.The mixing speed that polymer and solvent are mixed can be for example 100rmp~2000rmp, mixing time can be such as 100~200min.In certain embodiments, polymer can account for gained Such as the 30~99.99% of the mass fraction of slurry.
It is then possible to electron conductor material and/or electron-ion mixed conductor material are added into gained slurry, and It is stirred with so that they are equably mixed each other.The electron conductor material and/or electron-ion mixed conductor material added The percentage that material accounts for the gross mass of reaction cushion 130 can be such as 0.01%~70%.In some instances, mixing speed Can be such as 100rmp~2000rmp, mixing time can be such as 100~200min.
Here, the example of workable electron conductor material include but is not limited to carbon black, Ke Qin carbon (KB), acetylene black, Super P, graphene, single wall or multi-walled carbon nanotube, copper powder, aluminium powder, ruthenic oxide, molybdenum dioxide and theirs is any Combination.The example of workable electron-ion mixed conductor material includes but is not limited to native graphite, Delanium, soft carbon, hard Carbon, silicon, germanium, lithium titanate, titanium dioxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, tin oxide, stannous oxide, oxidation are sub- Silicon, iron sulfide, ferrous sulfide, Li3xLa2/3-xTiO3、LiZr2-yTiy(PO4)3、Li1+zAlzTi2-z(PO4)3、Li1+zAlzGe2-z (PO4)3、Li4-aGe1-aPaS4And their any combination, wherein 0≤x≤2/3,0≤y≤2,0≤z≤2,0≤a≤1.
Next, the slurry prepared can be coated in the table of negative electrode active layer 120 by coating machine or scraper On face, and dry, so as to form reaction cushion 130.The thickness of the reaction cushion 130 formed can be such as 0.05 μm~40 μm of scope, preferably in 1 μm~20 μm of scope.Although in the embodiment shown in Figure 1B, cushion 130 is reacted Negative electrode active layer 120 is continuously covered, but in further embodiments, reaction cushion 130 can also be covered discontinuously Negative electrode active layer 120.In addition, depending on used material, reaction cushion 130 can be porous layer or densification Layer.
In further embodiments, the slurry prepared can also be coated on the temporary carriers such as glass plate, release liners, And after drying, temporary carrier is removed so as to obtain the reaction cushion 130 of self-cradling type.Or it will can also prepare Good slurry is coated on the layer containing lithium metal 140 described below.Then, as hereinafter described, by the anti-of self-cradling type Cushion 130 or the reaction cushion 130 on layer containing lithium metal 140 is answered to be assembled into secondary cell secondary cell in other words Negative pole structure in.
Next, as shown in Figure 1 C, it can will contain lithium metal layer 140 and be arranged on reaction cushion 130, so as to form standard Negative pole structure 100.Layer containing lithium metal 140 can include such as lithium metal, Li-Si alloy, lithium-aluminium alloy, lithium boron alloy, lithium magnesium and close Gold or their any combination, and can be the forms such as the lamella, paillon foil, film layer of these materials.For example, it will can contain Lithium metal paillon foil 140 is placed on the top of reaction cushion 130, to form quasi- negative pole structure 100.As will be understood by those, can be with The parameters such as the thickness of layer containing lithium metal 140 are set according to the lithium amount needed for lithiation described below.For example, in some realities Apply in example, the thickness of layer containing lithium metal 140 can be such as 10nm-80 μm.In certain embodiments, layer containing lithium metal 140 can To be pantostrat；In further embodiments, layer containing lithium metal 140 can be discontinuous, such as can have through hole with exposure Reaction cushion 130 under it, through hole can have circle, rectangle, positive direction or other shapes, and the size or diameter of through hole Can be such as 10nm-5mm.
Then, reference picture 1D, quasi- negative pole structure 100 can be assembled into secondary cell together with positive pole 220, barrier film 230 In 200, its septation 230 can be between positive pole 220 and quasi- negative pole structure 100.Preferably, containing in quasi- negative pole structure 100 Lithium metal layer 140 is towards barrier film 230.As shown in figure iD, secondary cell 200 may include housing 210, positive pole 220, the and of barrier film 230 Quasi- negative pole structure 100 may be provided in housing 210.It should be understood that housing 210 can have it is variously-shaped, such as, but not limited to Cube, pancake etc., positive pole 220, barrier film 230 and quasi- negative pole structure 100 can also be assembled in housing 210 by various forms In.For example, positive pole 220, barrier film 230 and quasi- negative pole structure 100 can be alternate lamella, or the jellyroll of coiling (jelly roll) shape etc..Thus, the present invention is unrestricted.Positive pole 220 may be connected to positive terminal 214, accurate Negative pole structure 100 (in other words, collector 110 therein) may be connected to negative terminal 212.In further embodiments, it is accurate negative Pole structure 100 (in other words, collector 110 therein) can also be connected to metal shell 210, so as to which metal shell 210 serves as The negative terminal of battery 200.
In certain embodiments, the example available for the material for forming positive pole 220 includes but is not limited to cobalt acid lithium, mangaic acid Lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium-rich oxide, nickel ion doped, LiFePO4, lithium manganese phosphate, cobalt phosphate lithium, LiNiPO, lithium ferric manganese phosphate, ferric phosphate, manganese phosphate, cobalt phosphate, nickel phosphate, ferric metasilicate lithium, manganese silicate of lithium, cobaltous silicate lithium, silicon Sour nickel lithium, ferrosilite, manganous silicate, cobaltous silicate, silicic acid nickel and their any combination.In further embodiments, formed just The material of pole 220 also may be selected from manganese dioxide, iron sulfide, manganese sulfide, cobalt sulfide, nickel sulfide, titanium sulfide, ferric sulfate, ferric phosphate, Sulphur carbon and oxyvanadium compound and their any combination.
Barrier film 230 can include polymer film.The example of polymeric material for forming barrier film 230 includes but is not limited to Polypropylene, polyethylene, oxirane, PPOX, Kynoar, Kynoar-hexafluoropropene, polymethylacrylic acid Methyl esters, polyacrylonitrile, polyimides, PEI, makrolon, poly- aramid fiber, cellulose and their any combination. In certain embodiments, the thickness of barrier film 230 can be in 6-60 μm of scope, preferably in 6-25 μm of scope.In some realities Apply in example, barrier film 230 can be the porous circulation in favor of electrolyte, for example, barrier film 230 there can be 30%-90% hole Gap rate.
In certain embodiments, barrier film 230 may include the conductor coated at least one surface of above-mentioned polymer film Stratum granulosum, such as ion conductor stratum granulosum, nonionic conductive particles layer, electron conductor particles layer, ion-electron mixing conductor Granulosa and their any combination.The conductive particles layer can be coated on polymer film using bonding agent, and wherein bonding agent can Account for 70-99.9% percentage by weight.Moreover, the thickness of the conductive particles layer can be at such as, but not limited to 0.2-10 μm Scope.
Example available for the electronic conductor of the conductive particles layer of barrier film 230 include but is not limited to carbon black, Ke Qin carbon (KB), Acetylene black, Super P, graphene, single wall or multi-walled carbon nanotube, copper powder, aluminium powder, ruthenic oxide, molybdenum dioxide and they Any combination.
Example available for the ion-electron mixing conductor of the conductive particles layer of barrier film 230 includes but is not limited to natural stone Ink, Delanium, soft carbon, hard carbon, silicon, germanium, lithium titanate, titanium dioxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, oxidation Tin, stannous oxide, oxidation sub- silicon, iron sulfide, ferrous sulfide and their any combination.
Example available for the ion conductor of the conductive particles layer of barrier film 230 includes but is not limited to Li1+xAlxGe2-x (PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+xAlxTi2-x(PO4)3、Li4-aGe1-aPaS4、Li7-2b- cAbLa3Zr2-cBcO12、Li7-2d-2eAdLa3Zr2-eCeO12And their any combination, wherein 0≤x≤2,0≤y≤2/3,0 ≤ z≤2,0≤a≤1,0≤b≤5/2,0≤c≤2,0≤d≤3/2,0≤e≤2, element A are selected from Ge and Al, and B element is selected from Nb and Ta, C element are selected from Te and W.The average grain diameter of particle in ion conductor stratum granulosum can be in such as, but not limited to 10- 1000nm scope.
Example available for the nonionic conductor of the conductive particles layer of barrier film 230 includes but is not limited to nano aluminium oxide, received Rice silica, nano zine oxide, magnesia, calcium oxide, cerium oxide, zirconium oxide and their any combination.In some implementations In example, the particle diameter of nonionic conductive particles can be in 10-500nm scope.
It should be understood that the secondary cell assembled using the quasi- negative pole structure 100 shown in Fig. 1 C is not limited to shown in Fig. 1 D Structure, but can be the secondary battery construction of any existing or following exploitation.In the example secondary cell 200 shown in Fig. 1 D After being completed, electrolyte (not shown) can be injected into housing 210 with infiltration with the opening (not shown) on housing 210 Quasi- negative pole structure 100, positive pole 220 and barrier film 230.The volume range of the electrolyte injected in secondary cell 200 can be 1.5mL/Ah to 12mL/Ah, preferably 2mL/Ah are to 6mL/Ah.The temperature of the electrolyte of injection can be at -20 DEG C to 70 DEG C Scope, preferably ambient temperature, i.e., 20 DEG C or so；It can be 1-120 minutes to fill the time, after filling electrolyte, can be incited somebody to action Secondary cell 200 stands 1 minute to 24 hours, and dwell temperature can be -20 DEG C to 70 DEG C of scope, to retouch in detail below The lithiumation electrochemical reaction stated can be carried out fully.
Electrolyte used herein may include solvent and electrolyte.The example of solvent may be selected from methyl ethyl carbonate (EMC), Gamma-valerolactone (γ-VL), γ-fourth lactones (γ-BL), dimethyl carbonate (DMC), propene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate (EC), glycol dimethyl ether (DME), diethylene glycol dimethyl ether, TRIGLYME, tetraethylene glycol Dimethyl ether, 1,3- dioxolanes (DOL), tetrahydrofuran (THF), P13(the trifluoromethyl sulphur of TFSI, N- methyI-oropvD piperidines-two Acyl) inferior amine salt (PP13TFSI), (trimethyl fluoride sulfonyl) inferior amine salt of N- methyl-butvls piperidines-two (PP14TFSI), N- methyl-fourth (trimethyl fluoride sulfonyl) inferior amine salt of base pyrroles-two (PYR14TFSI), N- methyI-oropvDs pyrroles-two (trimethyl fluoride sulfonyl) imines Salt (PYR13TFSI), PEO and their any combination.Electrolyte can be such as lithium salts, and the example of lithium salts can Selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, double (trimethyl fluoride sulfonyls It is sub-) amine lithium, double fluorine sulfimide lithiums, di-oxalate lithium borate, lithium nitrate and their any combination.In certain embodiments, Concentration of the lithium salts in the electrolyte can be 0.01mol/L~3mol/L, it is therefore preferable to 0.01mol/L~1.5mol/L. When the electrolyte contains the lithium salts of above-mentioned concentration range, using the teaching of the invention it is possible to provide excellent electrical conductivity, and its cost is acceptable 's.
In certain embodiments, the electrolyte can also include boundary moisture agent, flame-retardant additive, film forming addition Agent or their any combination.Boundary moisture agent can effectively improve interface wellability, so as to promote foregoing lithiumation electrochemistry The progress of reaction；Flame-retardant additive can improve the security of secondary cell；And film for additive can then improve the boundary of battery Face stability.In some embodiments it may be preferred that the boundary moisture agent can be fluoro-ether, the flame-retardant additive can be with For phosphate, the film for additive can be selected from ethylene sulfite (ES), propylene sulfite (PS), vinylene carbonate (VC), dimethyl sulfite (DMS), diethyl sulfite (DES), 1,2- trifluoroacetic acid base ethane (BTE), ethylene carbonate Vinylene (VEC), fluorinated ethylene carbonate (FEC) and their any combination.
Describe the quasi- negative pole structure 100 shown in Fig. 1 C infiltrating the electrification afterwards occurred in the electrolytic solution referring to Fig. 1 E Learn reaction.As referring to figure 1E, when infiltration is in electrolyte (not shown), in the layer containing lithium metal 140 of quasi- negative pole structure 100 Lithium metal loses electronics, and becomes lithium ion 142, and lithium ion 142 can penetrate reaction cushion 130 and reach negative electrode active layer 120.At negative electrode active layer 120, lithium ion 142 reacts and obtained with the negative active core-shell material in negative electrode active layer 120 Electronics, it is embedded into so as to become lithium metal in negative electrode active layer 120, thus produces prelithiation negative pole 100'.Layer containing lithium metal Multiple rules or the through hole being randomly distributed are could be formed with 140, in order to which electrolyte permeates toward lower floor.In some embodiments In, after lithiumation electrochemical reaction is performed, the lithium metal in layer containing lithium metal 140 can have fully embedded into negative electrode active layer In 120, so as to which layer containing lithium metal 140 can be wholly absent；In further embodiments, perform lithiumation electrochemical reaction it Afterwards, part layer containing lithium metal 140 can also remains on reaction cushion 130, the lithium of residual, which can compensate secondary cell, to be made The lithium consumed with period, so as to improve the cycle characteristics of secondary cell.It can be set according to specific secondary cell type The parameters such as the thickness of layer containing lithium metal 140, lithiumation electrochemical reaction time, so as to control in the negative plate 100' of gained prelithiation The amount of the layer containing lithium metal 140 remained on reaction cushion 130.
It is understood that complete above-mentioned electrochemical reaction and feelings that layer containing lithium metal 140 partially or completely disappears Under condition, gap may be formed between barrier film 230 and reaction cushion 130, so that electric conductivity therebetween is deteriorated.At this In some embodiments of invention, as described above, by coating conductive particle layer on one or two surface of barrier film 230, can To improve the electric conductivity between barrier film 230 and adjacent layer, so as to which the problem be reduced or eliminated.On the other hand, lithium will can also be contained Metal level 140 is arranged to very thin, such as in 10nm to 15 μm of scope, preferably 10nm to 6 μm of scope, is given birth to so as to reduce Into gap, so as to improve electric conductivity.
Reaction cushion 130 can limit the speed of electrochemical reaction.As it was previously stated, reaction cushion 130 includes polymerization The lithium metal and negative electrode active that the mixture of thing and electronic conductor, wherein electronic conductor can be used in structure layer containing lithium metal 140 The electronics path between negative active core-shell material in layer 120 induces the progress of electrochemical reaction to form galvanic cell, and reacts slow The polymer rushed in layer 130 can increase the electronic resistance between layer containing lithium metal 140 and negative electrode active layer 120, so as to limit The size of lithiumation electric current, the reaction speed between lithium metal and negative active core-shell material is reduced, negative electrode active layer 120 is regulated and controled with this Embedding lithium speed and surface SEI films formation speed.So, can change on the basis of the coulombic efficiency first of negative pole is improved The cycle performance of kind negative pole.
In certain embodiments, the speed of lithiation can also be controlled by controlling the concentration of electrolyte.For example, can To make lithiation slowly, smoothly carry out using the electrolyte with low concentration., can be with after lithiation is completed The electrolyte of low concentration is replaced by the electrolyte of normal concentration to meet the needs of secondary cell normal operating.
Furthermore, it is possible to by controlling the lithium amount in layer containing lithium metal 140 effectively to regulate and control the lithiumation of negative electrode active layer 120 The raising degree of depth, i.e. initial coulomb efficiency.If the dosage of lithium metal exceedes the first all electrochemical reactions of negative active core-shell material The lithium and battery standing soak time long enough of consumption, then the open-circuit voltage of battery eventually drops to 0V, is now metal Lithium composite negative pole, and excessive lithium metal is irreversible during then progressively being discharged in follow-up cyclic process with replenishment cycles The lithium consumed is reacted, and the improvement of the initial coulomb efficiency of negative material and cycle performance is unaffected, and its later stage is followed The coulombic efficiency of ring will reach or even only slight beyond 100%.
Above-mentioned galvanic interaction process, the i.e. activation process of secondary cell 200, can be as previously described in time of repose section Carry out, directly can also be completed during the energization use of secondary cell 200.After reaction is completed, that is, generate prelithiation Negative pole 100', as referring to figure 1E, wherein can include or not comprising remaining layer containing lithium metal 140.Next, it can also use The method for vacuumizing and heating removes the organic solvent in secondary cell 200, and wherein vacuum can be 1-10000Pa, add Hot temperature can be such as 30 DEG C -280 DEG C, preferably 60 DEG C -80 DEG C, to complete the making of secondary cell 200.
In embodiment described above, quasi- negative pole structure 100 is assembled into secondary cell 200, is then injected into electrolysis Liquid facilitates electrochemical reaction, so as to complete prelithiation negative pole 100' preparation in secondary cell 200.This embodiment pair It is preferably as secondary battery industry production line can be provided for lithium metal for industrially manufacture secondary cell The operating environment of safety, and technological process is compact, so as to save cost.But, if it is desired, can not also be by quasi- negative pole Structure 100 is assembled into secondary cell 200, but is directly dipped in electrolyte, completes prelithiation negative pole 100' system It is standby, then prelithiation negative pole 100' is assembled into secondary cell 200 again.It should be noted that ought be individually by quasi- negative pole structure 100 When immersing in electrolyte, safe environment for lithium metal, such as the atmosphere of inactive gas should be provided, because working as lithium metal It can be reacted when being exposed to air, its surface can form one layer of lithium carbonate.In addition, it is also desirable to provide exhaust treatment system is to locate Quasi- negative pole structure 100 is immersed caused a large amount of excitant waste gas and electrolyte volatilization gas in electrolyte by reason.
The lithiation of above-mentioned lithium ion battery negative material passes through in the whole face coating in the surface of negative electrode active layer 120 or portion Coating reaction cushion 130 is divided to limit lithiumation size of current, the galvanic cell adjusted between lithium metal and negative active core-shell material is anti- Speed is answered, the formation speed of the embedding lithium speed of negative active core-shell material and surface SEI films is regulated and controled with this, so as to improve negative pole work On the basis of the coulombic efficiency first of property material, improve the cycle performance of negative active core-shell material.The technique stream of embodiment description Journey is simple, easily operated, and is very suitable for the lithiumation of commercial Li-ion battery negative material, supplements because of irreversible reaction The lithium of consumption, so as to improve coulombic efficiency first, the capacity of secondary cell, and improve its cycle performance.
It should be understood that due to the negative pole of lithium rechargeable battery and sodium ion secondary battery can use it is substantially similar Negative pole, barrier film and electrolyte, sodium principle is also similar, and simply the sodium salt in sodium ion secondary battery is sodium hexafluoro phosphate, high chlorine Sour sodium, trifluoromethyl sulfonate, methyl fluoride sodium sulfonate, double (trimethyl fluoride sulfonyl is sub-) amine sodium, double fluorine sulfimide sodium etc., positive pole For sodium manganate, cobalt acid sodium, sodium pyrophosphate, sodium monofluorophosphate, Prussian blue etc..Therefore, principle of the invention and it is above-mentioned and its His embodiment may apply to sodium ion secondary battery, and under the teachings of the present invention, this application is for this area skill It is obvious for art personnel.In embodiments of the invention and appended claims, described lithium ion secondary Battery is interpreted as being intended to be also covered by sodium ion secondary battery.
Fig. 2 shows the prelithiation negative pole and secondary cell according to another embodiment of the present invention manufactured for secondary cell Method an interstage.As described in Figure 2, except sequentially forming the first negative electrode active on the first surface of collector 110 Layer 120, first is reacted outside the layer containing lithium metal 140 of cushion 130 and first, also in the opposite with first surface of collector 110 Second surface on sequentially form the second negative electrode active layer 150, second reaction the layer containing lithium metal 170 of cushion 160 and second.Cause This, when immersing in the electrolytic solution, occurs galvanic interaction between the second layer containing lithium metal 170 and the second negative electrode active layer 150, So that lithium metal 172 can be embedded into the second negative electrode active layer 150.Other aspects of embodiment illustrated in fig. 2 can be with Figure 1A -1E Shown embodiment is identical, and description is not repeated herein.
It should be understood that in certain embodiments, secondary cell may include the prelithiation negative pole of the bilateral structure shown in Fig. 2 Both with the prelithiation negative pole of single-sided structure shown in Fig. 1 E.For example, in conventional laminated construction, the prelithiation positioned at centre Negative pole may include the bilateral structure shown in Fig. 2, and the prelithiation negative pole positioned at both ends may include the single-sided structure shown in Fig. 1 E.When So, the invention is not restricted to the example, but single-sided structure and any combination of bilateral structure can be used.
Some examples of the present invention are described below.
Example 1
Conventional method is first according to, graphite cathode active material is coated on the surface of copper current collector, face amount is 3mAh/ cm2。
Next reaction cushion is prepared.0.98g poly- inclined fluorine is added in 9g 1-METHYLPYRROLIDONE (NMP) solution Ethene (PVDF), 30min is stirred with 1000rpm rotating speed in agitator.After PVDF is completely dissolved, 0.02g Ke is added Qin carbon (KB), continue to stir 100min with 800rpm rotating speed, prepare uniform reaction cushion slurry.Next, using Slurry is coated on the surface of negative electrode active layer by 50 μm of scraper, is then placed in 55 DEG C of drying box and is toasted 24h.Made Into diameter 14mm pole piece, it is placed in 120 DEG C of vacuum drying chamber and continues to toast 6h.
Then, in specific environment such as glove box, according to metal, barrier film, piece containing lithium metal (20 μ m-thicks, diameter 2mm), The order of above-mentioned pole piece is assembled into secondary cell, and adds the μ L of commercial li-ion battery electrolyte 120, and it includes 0.6mol's LiPF6And organic solvent, organic solvent 1:1 DMC:EC.Battery container can use CR2032.Secondary cell can be placed on Battery open circuit voltage is tested on blue electrical measurement test system, lithiation speed is judged by cell voltage.
Compare in addition, including the secondary cell without the graphite cathode for reacting cushion according further to above-mentioned steps assembling and being used as Example.Fig. 3 shows the relation curve that the voltage of the secondary cell of above-mentioned example 1 and the secondary cell of the comparative example changes over time. As shown in figure 3, the voltage decline of the secondary cell of example 1 is slower than comparative example, thus at same time point with higher Voltage.
Table 1 below illustrates the efficiency for charge-discharge data of three kinds of secondary cells, these three secondary cells include mark respectively Meta anthracite negative pole, the prelithiation graphite cathode without reaction cushion and according to an embodiment of the invention utilize react slow Rush the prelithiation negative pole of layer.
Table 1：Efficiency for charge-discharge
1 week (%) 2 weeks (%) 3 weeks (%) 15 weeks (%)
Standard graphite 91.3 99.2 99.4 99.9
Reactionless cushion - 92.6 99.7 99.8
There is reaction cushion - 99.1 99.5 99.9
As it can be seen from table 1 have reaction cushion secondary cell efficiency for charge-discharge almost with the first cycle directly The efficiency for charge-discharge of the Standard graphite secondary cell of Electrochemical lithiation is identical, the charge and discharge of the secondary cell without reacting cushion Electrical efficiency is relatively low.
Fig. 4 shown after lithiumation 48 hours, surface scan Electronic Speculum (SEM) photo of the prelithiation negative pole of example 1.Such as figure Shown in 4, layer containing lithium metal 140 substantially completely disappears, and can only see reaction cushion 130.
Example 2
Conventional method is first according to, the mixing negative electrode active material of the sub- silicon of coating oxidation and graphite on the surface of copper current collector Material, the capacity of the material is 600mAh/g, and the face amount of coating is 3mAh/cm2。
Next reaction cushion is prepared.0.99g polypropylene is added in 9g 1-METHYLPYRROLIDONE (NMP) solution Nitrile (PAN), 30min is stirred with 1000rpm rotating speed in agitator.After PAN is completely dissolved, 0.01g acetylene black is added, Continue to stir 100min with 800rpm rotating speed, prepare uniform reaction cushion slurry.Next, using 50 μm of scraper Slurry is coated on the surface of negative electrode active layer, is then placed in 55 DEG C of drying box and toasts 24h.It is made into diameter 14mm Pole piece, be placed in 120 DEG C of vacuum drying chamber continue toast 6h.
Then, in specific environment such as glove box, according to metal, barrier film, piece containing lithium metal (20 μ m-thicks, diameter 2mm), The order of above-mentioned pole piece is assembled into secondary cell, and adds the μ L of commercial li-ion battery electrolyte 120, and it includes 1mol's LiPF6And organic solvent, organic solvent 1:1 DMC:EC.Battery container can use CR2032.Secondary cell can be placed on Battery open circuit voltage is tested on blue electrical measurement test system, lithiation speed is judged by cell voltage.
Battery assembles：In order to judge lithiumation speed, we pass through according to metal, barrier film, lithiated metal lithium piece (20um thickness) Diameter 2mm, lithiated metal lithium piece (250um thickness) diameter 2mm, the oxidation Asia silicon composite graphite of coating lithiation delay layer are born Pole adds commercial li-ion battery electrolyte 120uL, DEC simultaneously:EC=1:1,1mol LiPF6 electrolyte assembled batteries.Battery Shell uses CR2032.Lithiation speed is judged by cell voltage.Battery is placed on blue electrical measurement test system and tests battery open circuit Voltage.
In addition, include the secondary of the sub- 3 SiC 2/graphite mixing negative pole of oxidation without reaction cushion according further to above-mentioned steps assembling Battery is as comparative example.Table 2 below shows the efficiency for charge-discharge data of three kinds of secondary cells, these three secondary cells difference The sub- 3 SiC 2/graphite mixing negative pole of oxidation including standard, the sub- 3 SiC 2/graphite mixing negative pole of prelithiation oxidation without reaction cushion, with And the sub- 3 SiC 2/graphite mixing negative pole (that is, example 2) of prelithiation oxidation of cushion is reacted in utilization according to an embodiment of the invention.
Table 2：Efficiency for charge-discharge
1 week (%) 2 weeks (%) 3 weeks (%) 4 weeks (%)
Aoxidize sub- 3 SiC 2/graphite mixing negative pole 79.15 96.95 98.07 98.56
Reactionless cushion - 95.08 96.5 97.15
There is reaction cushion - 96.95 98 98.47
From table 2 it can be seen that the efficiency with reaction cushion is almost identical with the efficiency of the embedding lithium of Direct Electrochemistry, and do not have There is the efficiency of reaction cushion then relatively low.
Example 3-30
Example 3-30 is the reaction cushion being used together with negative active core-shell material according to some embodiments of the invention Example.As it was previously stated, reaction cushion includes polymer and electronic conductor, electronic conductor described herein covers electron-ion Mixed conductor.
The polymer that reaction cushion includes can be from following middle selection：Polymer 1, Vingon (PVDF)；Polymerization Thing 2, Vingon-hexafluoropropene (PVDF-HFP)；Polymer 3, polytetrafluoroethylene (PTFE) (PTFE)；Polymer 4, polyoxyethylene Alkene；Polymer 5, polyester；Polymer 6, polyamide；Polymer 7, polymethyl methacrylate；Polymer 8, makrolon；Polymerization Thing 9, carboxymethyl cellulose；Polymer 10, SB；Polymer 11, polyacrylonitrile；Polymer 12, carboxylic first Base sodium cellulosate, polymer 13, sodium carboxymethylcellulose:SBR styrene butadiene rubberses=1:1；Polymer 14, polyacrylic acid； Polymer 15, Lithium polyacrylate.
The electronic conductor that reaction cushion includes can be from following middle selection：Electronic conductor 1, carbon black；Electronic conductor 2, Ke Qin carbon (KB)；Electronic conductor 3, acetylene black；Electronic conductor 4, silicon；Electronic conductor 5, graphene；Electronic conductor 6, aluminium powder；Electronics is led Body 7, single wall or multi-walled carbon nanotube；Electronic conductor 8, Li1+xAlxGe2-x(PO4)3, 0≤x≤2；Electronic conductor 9, Delanium； Electronic conductor 10, hard carbon；Electronic conductor 11, soft carbon；Electronic conductor 12, LiZr2-xTix(PO4)3, 0≤x≤2；Electronic conductor 13, Ke Qin carbon:LiZr2-xTix(PO4)3=1:1 (mass ratio), 0≤x≤2；Electronic conductor 14, Ke Qin carbon:Li1+xAlxTi2-x(PO4)3 =1:1 (mass ratio), 0≤x≤2；Electronic conductor 15, lithium titanate；Electronic conductor 16, lithium titanate:Silicon=1:1.
The negative active core-shell material that negative electrode active layer includes can be from following middle selection：Negative active core-shell material 1, hard carbon；Negative pole Active material 2, graphite；Negative active core-shell material 3, silicon；Negative active core-shell material 4, aoxidize sub- silicon；Negative active core-shell material 5, silicon/carbon are multiple Compound；Negative active core-shell material 6, aoxidize sub- silicon/carbon complex；Negative active core-shell material 7, hard carbon/graphite composite；Negative electrode active material Material 8：Soft carbon.
Table 3 shows negative electrode active layer used in example 3-34 and reacts the material of cushion.
Table 3, lithiation cushion composition
Experiment shows that the reaction cushion in above-mentioned example can play good effect so that corresponding secondary electricity Pond has the coulombic efficiency first improved and the cycle performance significantly improved.
Example 31-34
As it was previously stated, the invention further relates to pre- sodium negative pole, example 31-34 is the negative active core-shell material for natridization reaction With the example of reaction cushion.The negative active core-shell material that is used in example 31-34 and reaction cushion can also be from being listed above Material in select, used material has been shown in particular in table 4 below.
Table 4, natridization reaction cushion composition
Experiment shows that the reaction cushion in above-mentioned example can play good effect so that corresponding pre- sodium Secondary cell has the coulombic efficiency first improved and the cycle performance significantly improved.
Example 35
Example 35 is the lithium rechargeable battery prepared by lithiumation, and specific manufacturing process is as follows.
Positive pole uses cobalt acid lithium, and negative pole uses the negative pole of the structure of embodiment 3, barrier film using dual coating aluminum oxide PP every Film, secondary cell is assembled into safe atmosphere, then such as electrolyte.Electrolyte in electrolyte is LiPF6, concentration is 1mol/L, organic solvent 1:1 EC:DMC.After injecting electrolyte, secondary cell is stood 24 hours to complete lithiumation.
In addition, the comparative example of example 35 has been also prepared for it.In the comparative example, not comprising reaction cushion, other aspect with Example 35 is identical.
Constant current charge-discharge cycle of modes test, charge cutoff voltage 4.35V, electric discharge cut-off electricity are carried out using discharge and recharge instrument Press as 3.0V, test and carried out under 0.2A current strength, test temperature is 25 DEG C.Fig. 5 A show the charge and discharge cycles of comparative example Curve, Fig. 5 B show the charge and discharge cycles curve of example 35.Reference picture 5A and 5B can be seen that the head of the secondary cell of comparative example All volumetric efficiencies are very low, and capacity attenuation is a lot；And the secondary cell of example 35 has higher first all volumetric efficiencies, and capacity Decay is also much smaller.In addition, the uniformity of the curve shown in Fig. 5 B will be substantially better than the uniformity of the curve shown in Fig. 5 A, table The secondary cell for expressing example 35 has the circulation uniformity significantly improved compared with the secondary cell of comparative example.
Example 36-70
Example 36-70 is the example according to the secondary cell of some embodiments of the present invention.Made in these secondary cells Material can select from following list of materials.
Workable electrolyte includes but is not limited in electrolyte：Lithium salts 1, LiPF6；Lithium salts 2, LiN (CF3SO2)2；Lithium salts 3, LiBF4；Lithium salts 4, LiClO4；Lithium salts 5, LiCF3SO3；Lithium salts 6, Li (CF3SO2)3；Lithium salts 7, LiNO3；Lithium salts 8, LiAsF6； Lithium salts 9, LiBOB；Sodium salt 10, NaPF6。
Workable solvent includes but is not limited in electrolyte：Solvent 1, DME:DOL=1:1；Solvent 2, PC；Solvent 3, DEC；Solvent 4, DMC；Solvent 5, PP13TFSI；Solvent 6, PYR13TFSI；Solvent 7, TEGDME (TRIGLYME)；Solvent 8, EC:DEC=1:1；Solvent 9, EC:DMC=1:1.
Workable positive electrode includes but is not limited to：Positive electrode 1, cobalt acid lithium；Positive electrode 2, LiFePO4；Positive pole Material 3, LiMn2O4；Positive electrode 4, nickle cobalt lithium manganate；Positive electrode 5, nickel cobalt lithium aluminate；Positive electrode 6, lithium-rich oxidation Thing；Positive electrode 7, nickel ion doped；Positive electrode 8, MnO2；Positive electrode 9, FeS2；Positive electrode 10, FeF3；Positive electrode 11, S；Positive electrode 12, ferric phosphate；Positive electrode 13, phosphoric acid ferrimanganic；Positive electrode 14, O2；Positive electrode 15：O2+CO2；Just Pole material 16, sodium manganate.
Table 5 shows the concrete structure of the secondary cell in example 36-70
Table 5, the structure of secondary cell
Experiment shows that these secondary cells can work, and have well within the temperature range of -10 DEG C to 45 DEG C There are improved first all charge efficiencies and cycle performance.
While certain embodiments of the invention have been described, but these implementations are presented simply by means of example Example, and the embodiment is not intended to limit the scope of the present invention.Indeed, it is possible to implement to retouch here according to various other forms The novel method and device stated；Furthermore, it is possible to make the various provinces in the form and details of method and apparatus described here Slightly, substitute and change, without departing from the principle of the present invention.Accompanying claims and its equivalent are intended to fall into the present invention's These in thought and scope are omitted, substitute and changed.

Claims (12)

1. a kind of manufacture method of prelithiation negative pole for secondary cell, including：
The first negative electrode active layer and the first reaction cushion are sequentially formed on the first surface of collector；
The first layer containing lithium metal is set to obtain quasi- negative pole structure on the described first reaction cushion；And
By the quasi- negative pole structure leaching in the electrolytic solution, make between first layer containing lithium metal and the first negative electrode active layer Generation electrochemical reaction, so as to which the lithium in first layer containing lithium metal is embedded into the negative electrode active of the first negative electrode active layer To form prelithiation negative pole in material.
2. the method for claim 1, wherein before by the quasi- negative pole structure leaching in the electrolytic solution, methods described Also include the quasi- negative pole structure being assembled into secondary cell together with positive pole, barrier film, wherein the barrier film be arranged on it is described Between quasi- negative pole structure and the positive pole.
3. method as claimed in claim 2, wherein, it is secondary the quasi- negative pole structure is assembled into together with positive pole, barrier film Before in battery, methods described also includes：
The second negative electrode active layer and second are sequentially formed on the second surface opposite with the first surface of the collector React cushion；And
The second layer containing lithium metal is set on the described second reaction cushion,
Wherein, when by the quasi- negative pole structure leaching in the electrolytic solution, second layer containing lithium metal is lived with second negative pole Property layer between electrochemical reaction occurs, so as to which the lithium in second layer containing lithium metal is embedded into the second negative electrode active layer In negative active core-shell material.
4. method as claimed in claim 3, wherein, it is every in the first reaction cushion and the second reaction cushion It is individual including at least one of electron conductor material and electron-ion mixed conductor material and polymer,
Wherein, the electron conductor material is received including carbon black, Ke Qin carbon, acetylene black, Super P, graphene, single wall or more wall carbon Mitron, copper powder, aluminium powder, native graphite, Delanium, soft carbon, hard carbon, siliceous, tin, germanium, zinc, aluminium, boron, magnesium elements material, Molybdenum dioxide and their any combination,
Wherein, the electron-ion mixed conductor material native graphite, Delanium, soft carbon, hard carbon, silicon, germanium, lithium titanate, two Titanium oxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, tin oxide, stannous oxide, the sub- silicon of oxidation, iron sulfide, ferrous sulfide, Li3xLa2/3-xTiO3、LiZr2-yTiy(PO4)3、Li1+zAlzTi2-z(PO4)3And their any combination, 0≤x≤2/3,0≤ y≤2,0≤z≤2,
Wherein, the polymer includes Vingon PVDF, Vingon-hexafluoropropene PVDF-HFP, polytetrafluoroethylene (PTFE) PTFE, polyethylene glycol oxide, polyester, polyamide, polyamidoimide, polymethyl methacrylate, makrolon, carboxymethyl cellulose Element, SB, polyacrylic acid, Lithium polyacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-styrene rubber with And their any combination,
Wherein, the mass percent shared by the polymer is 30%~99.99%, the electron conductor material and the electricity Mass percent shared by son-ion mixed conductor material is 0.01%~70%,
Wherein, lithium metal, Li-Si alloy, lithium are each included in first layer containing lithium metal and second layer containing lithium metal Aluminium alloy, lithium boron alloy, lithium magnesium alloy and their any combination, and
Wherein, scope of the concentration of the electrolyte in 0.01mol/L~3mol/L.
5. method as claimed in claim 3, wherein, it is every in the first reaction cushion and the second reaction cushion Scope of the individual thickness at 0.05 μm to 40 μm,
Wherein, in the first reaction cushion and the second reaction cushion it is each pantostrat or discontinuity layer,
Wherein, it is described first reaction cushion and it is described second reaction cushion in be each it is porous or fine and close,
Wherein, model of each thickness in first layer containing lithium metal and second layer containing lithium metal at 10nm-80 μm Enclose,
Wherein, first layer containing lithium metal and second layer containing lithium metal respectively partially or fully cover described first Cushion and the second reaction cushion are reacted, and
Wherein, in first layer containing lithium metal and second layer containing lithium metal be each pantostrat or with through hole with Expose the first reaction cushion under it and the second reaction cushion.
6. a kind of prelithiation negative pole for secondary cell, including：
Collector；
The first negative electrode active layer being arranged on the first surface of the collector；And
The first reaction cushion being arranged on the first negative electrode active layer,
Wherein, the negative active core-shell material of the first negative electrode active layer is through the first reaction cushion lithiumation.
7. prelithiation negative pole as claimed in claim 6, in addition to：
The second negative electrode active layer being arranged on the second surface opposite with the first surface of the collector；And
The second reaction cushion being arranged on the second negative electrode active layer,
Wherein, the negative active core-shell material of the second negative electrode active layer is through the second reaction cushion lithiumation.
8. a kind of method for manufacturing secondary cell, including：
The first negative electrode active layer and the first reaction cushion are sequentially formed on the first surface of collector；
The first layer containing lithium metal is set to obtain quasi- negative pole structure on the described first reaction cushion；
The quasi- negative pole structure is assembled into secondary cell together with positive pole, barrier film, wherein the barrier film is arranged on the standard Between negative pole structure and the positive pole；And
Electrolyte is injected into the secondary cell, makes to send out between first layer containing lithium metal and the first negative electrode active layer Raw electrochemical reaction, so as to which the lithium in first layer containing lithium metal is embedded into the negative electrode active material of the first negative electrode active layer To form prelithiation negative pole in material.
9. method as claimed in claim 8, wherein, it is secondary the quasi- negative pole structure is assembled into together with positive pole, barrier film Before in battery, methods described also includes：
The second negative electrode active layer and second are sequentially formed on the second surface opposite with the first surface of the collector React cushion；And
The second layer containing lithium metal is set on the described second reaction cushion.
10. a kind of secondary cell, including：
Housing；And
Positive pole, barrier film and the prelithiation negative pole being arranged in the housing, the barrier film are located at the positive pole and the prelithiation Between negative pole, the prelithiation negative pole includes：
Collector；
The first negative electrode active layer being arranged on the first surface of the collector；And
The first reaction cushion being arranged on the first negative electrode active layer,
Wherein, the first negative electrode active layer is through the first reaction cushion lithiumation.
11. secondary cell as claimed in claim 10, wherein, the prelithiation negative pole also includes：
The second negative electrode active layer being arranged on the second surface opposite with the first surface of the collector；And
The second reaction cushion being arranged on the second negative electrode active layer,
Wherein, the second negative electrode active layer is through the second reaction cushion lithiumation.
12. secondary cell as claimed in claim 10, wherein, the barrier film includes：
Polymer film；And
Conductive particles layer at least one surface coated in the polymer film, the conductive particle layer include ion conductor Particle, electron conductor particles, ion-electron mixing conductor particle or their any combination.
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