CN105762326A - Lithium battery and preparation method thereof - Google Patents
Lithium battery and preparation method thereof Download PDFInfo
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- CN105762326A CN105762326A CN201410791171.0A CN201410791171A CN105762326A CN 105762326 A CN105762326 A CN 105762326A CN 201410791171 A CN201410791171 A CN 201410791171A CN 105762326 A CN105762326 A CN 105762326A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a lithium battery and a preparation method thereof, and specifically discloses a lithium battery, the lithium battery includes a positive electrode, a negative electrode, a separator, an electrolyte and a housing, the negative electrode contains a negative electrode material or comprises the following negative electrode material, the negative electrode material comprises a support structure and a lithium-ion / lithium metal storage layer coating one side of the support structure, the electrolyte contains a film-forming additive, and a polymer interface protective layer is formed by the film-forming additive on the lithium-ion / lithium metal storage layer. The present invention also discloses the preparation method of the lithium battery. The lithium battery prepared by the preparation method has excellent lithium metal storage function, can inhibit lithium metal dendritic growth, make electrode interface current density uniform in distribution, maintain electrodes surface low interface impedance and other series characteristics for optimization of electrode cycle efficiency and service life.
Description
Technical field
The present invention relates to electrochemical energy storage field, more particularly to a kind of lithium battery and preparation method thereof.
Background technology
Lithium ion battery and secondary lithium metal battery are all paid close attention to widely in battery industry all the time as efficient mobile energy storage device and are greatly developed, simultaneously worldwide, academia is still regarded as hot technology and carries out furtheing investigate with seeking breakthrough and development.
As a kind of high-energy-density negative material, (lithium theoretical metal capacity is 3860mAh/g to lithium metal, and there is minimum electrode potential) at lithium air, application prospect in the emerging high energy-storage battery systems such as lithium sulfur is unanimously had an optimistic view of, but cycle efficieny is relatively low, safety is bad etc., and problem hampers its further genralrlization in battery industry and application always.Being found by substantial amounts of research, in battery charging process, lithium metal surface can produce uneven lithium deposition.Along with lasting charging process, uneven lithium deposition inevitably leads to the local lithium dendrite growth of lithium metal surface.Dendrite problems can cause that electrode interface impedance increases, battery capacity loss.Lasting dendritic growth can pierce through electrolyte barrier film and cause battery short circuit, make lithium an-ode in use all the time along with huge potential safety hazard, this also makes it be difficult to be applied to such as electric motor car, and safety coefficient is required in higher working environment by accompanied electronic equipment etc..
The various solutions proposed by industry in recent years, the service life of lithium an-ode and efficiency be improved significantly, but improve intensity and still be difficult to meet the demand of large-scale commercial.Wherein, by lithium metal surface carbon coating material, although lithium dendrite growth mechanism can be improved to a certain extent, but the mechanical performance of carbon layer material is poor, easily break.By being coated with oxide in lithium metal surface, although the mechanical strength of material can be improved, but the growth mechanism of Li dendrite cannot be improved.Use solid electrolyte to grow by dendrite inhibition to a certain extent, but relatively low ionic conductivity and poor electrode/electrolyte contact interface all can cause that the internal resistance of cell increases considerably.
Additionally, have benefited from the lithium reversible embedding in graphite material and deviate from, Li dendrite can be avoided in running in the generation of negative terminal surface with the lithium ion battery that graphite is negative material.Although graphite cathode material energy density is relatively low (is 339mAh/g in lithium embedding situation, lithium is deviate from situation for 372mAh/g), lithium ion battery has still brought more stable cycle efficieny and service life by sacrifice high-energy-density, and relatively low potential safety hazard, and successfully realize commercialization.But under nonstandard charge and discharge system, dendrite still can grow at graphite surface, and increase graphite electrode impedance and even result in graphite-structure breakage.
Described in summary, although the method having had multiple protection Li dendrite at present, but protection effect is all still unsatisfactory, therefore, this area is in the urgent need to developing a kind of lithium battery and preparation technology thereof that can have and suppress Li dendrite and the maintenance low interface impedance of electrode surface simultaneously.
Summary of the invention
It is an object of the invention to provide a kind of lithium battery that can have simultaneously suppress Li dendrite and the maintenance low interface impedance of electrode surface and preparation method thereof.
In a first aspect of the present invention, provide a kind of lithium battery, described lithium battery includes positive pole, negative pole, barrier film, electrolyte and shell, described negative pole contains following negative material or is made up of following negative material, described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side, wherein, described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent, described electrolyte contains film for additive, and described film for additive forms polymer interface protective layer on lithium ion/lithium metal accumulation layer.
In another preference, described ceramic oxide is selected from lower group: Al2O3、ZrO2、SiO2, or its combination.
In another preference, described material with carbon element is selected from lower group: carbon black, graphite, charcoal granule, carbon nanotube, Graphene or its combination.
In another preference, described material with carbon element is special close high connductivity carbon black (Super-P).
In another preference, described binding agent is selected from lower group: tertiary benzene butyl rubber, polyimides, polyacrylate, sodium alginate or its combination.
In another preference, described supporting construction is selected from lower group: Copper Foil, copper mesh, lithium paper tinsel, nickel screen.
In another preference, in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide, material with carbon element and binding agent three is 30～97.5:0.5～20:2～50.
In another preference, in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide and material with carbon element is 60～99.5:0.5～40.
In another preference, in described lithium ion/lithium metal accumulation layer, the content of material with carbon element is 0.5～20%, it is preferred to 0.5～10%；And/or binder content is 2～50%, it is preferred to 10～20%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
In another preference, in described lithium ion/lithium metal accumulation layer, the content of ceramic oxide is 30～97.5%, it is preferred to 30～80%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
In another preference, described film for additive content in the electrolytic solution be 1～300 mmoles/liter, it is preferred to 1～50 mmoles/liter.
In another preference, described film for additive is selected from lower group: isocyanates additive, carbonate ester additive, fluoro-ether additive or its combination.
In another preference, described isocyanates additive is hexamethylene diisocyanate (HDI).
In another preference, the thickness of described lithium ion/lithium metal accumulation layer is 10～100 μm.
In another preference, the thickness of described lithium ion/lithium metal accumulation layer is preferably 50-100 μm, is more preferably 70-80 μm.
In another preference, the thickness of described polymer interface protective layer is 1～10nm, is more preferably 4-6nm.
In another preference, the particle diameter of described material with carbon element is 40nm～40 μm.
In another preference, the particle diameter of described material with carbon element is 100-1000nm, it is preferred to 400-600nm.
In another preference, the particle diameter of described ceramic oxide is 10～100nm.
In another preference, the particle diameter of described ceramic oxide is 20-50nm, it is preferred to 30-40nm.
In another preference, described supporting construction is lithium sheet.
In a second aspect of the present invention, it is provided that the preparation method of the lithium battery described in a kind of first aspect present invention, including step:
(a-1) positive pole, negative pole, barrier film, electrolyte and shell are provided；
Wherein, described negative pole contains following negative material or is made up of following negative material; described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side; described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent; containing film for additive in described electrolyte, and described film for additive forms polymer interface protective layer on described lithium ion/lithium metal accumulation layer；
(a-2) described positive pole, negative pole, barrier film, electrolyte and shell are assembled the lithium battery formed described in first aspect present invention.
In another preference, described in be assembled under inert gas shielding to carry out.
In another preference, the preparation process of described negative material is as follows:
(b-1) binding agent is dissolved in advance in organic solvent and obtains binder solution；
(b-2) material with carbon element, ceramic oxide and binder solution are mixed in organic solvent acquisition negative material slurry；
(b-3) negative material slurry being coated on supporting construction one side, baking forms the negative pole with lithium ion/lithium metal accumulation layer.
In another preference, described organic solvent is selected from lower group: N-Methyl pyrrolidone (NMP), DMF (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO).
In another preference, described organic solvent is N-Methyl pyrrolidone (NMP).
In another preference, described step (b-1) and/or (b-2) carry out under stirring.
In another preference, described stirring is magnetic agitation.
In another preference, in described step (b-1) and/or (b-2), the time of stirring is 0.1～5 hour, it is preferred to 1～3 hour.
In another preference, described baking carries out under vacuum environment or inert gas shielding.
In another preference, described baking temperature is 80～140 DEG C, is more preferably 100～120 DEG C.
In another preference, described baking time is 0.5～20h, is more preferably 3～15h.
In another preference, described electrolyte is under inert gas shielding, is added in commercial electrolyte liquid by described film for additive and obtains.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme.As space is limited, tired no longer one by one state at this.
Accompanying drawing explanation
Fig. 1 is that the present invention includes supporting construction and the schematic diagram of the negative material of the polymer interface protective layer being positioned at the lithium ion on described supporting construction/lithium metal accumulation layer and formed on lithium ion/lithium metal accumulation layer by electrolyte film for additive.
Fig. 2 is the charge and discharge cycles curve of the Copper Foil battery 1 of the embodiment of the present invention 1 preparation.
Fig. 3 is the charge and discharge cycles curve of the Copper Foil battery C1 of comparative example 1 of the present invention preparation.
Fig. 4 is the charge and discharge cycles curve of the Copper Foil battery C2 of comparative example 2 of the present invention preparation.
Fig. 5 is the charge and discharge cycles curve of the Copper Foil battery C3 of comparative example 3 of the present invention preparation.
Fig. 6 is the charge and discharge cycles curve of the Copper Foil battery C4 of comparative example 4 of the present invention preparation.
Fig. 7 is the interface impedance contrast of the Copper Foil battery of the embodiment of the present invention 1 and comparative example 1,2,3 and 4 preparation.
Fig. 8 is the Electronic Speculum figure contrast before and after the embodiment of the present invention 1 charge and discharge cycles.
Fig. 9 is the Electronic Speculum figure contrast before and after comparative example 3 charge and discharge cycles of the present invention.
Detailed description of the invention
The present inventor is through long-term and deep research, by on supporting construction surface, coated ceramic oxide and material with carbon element prepare negative material simultaneously, commercial electrolyte liquid adds specific film for additive and prepares electrolyte, and described negative material and electrolyte and general positive pole, barrier film and shell are assembled, unexpectedly it is prepared for a kind of there is good lithium metal memory function, suppress the growth of lithium metallic dendrite, make the distribution of electrode interface uniform current density, maintain the lithium battery of the performances such as the low interface impedance of electrode surface.Based on above-mentioned discovery, inventor completes the present invention.
Term
In the present invention, " supporting construction " and " support structure layers " is used interchangeably, and refers both to be selected from the material of lower group: Copper Foil, copper mesh, lithium paper tinsel, nickel screen.
In the present invention, " lithium ion/lithium metal accumulation layer ", " high mechanical properties accumulation layer " and " accumulation layer " are used interchangeably, and refer both to the accumulation layer containing ceramic oxide, material with carbon element and binding agent.
Negative material and preparation method thereof
In the present invention, described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side, and wherein, described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent.
Typically, described ceramic oxide includes (but being not limited to): Al2O3、ZrO2、SiO2, or its combination.
Typically, described material with carbon element includes (but being not limited to): carbon black, graphite, charcoal granule, carbon nanotube, Graphene or its combination.
Specifically, described material with carbon element is special close high connductivity carbon black (Super-P).
Typically, described binding agent includes (but being not limited to): tertiary benzene butyl rubber, polyimides, polyacrylate, sodium alginate or its combination.
In a preference, in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide, material with carbon element and binding agent three is 30～97.5:0.5～20:2～50.
Specifically, in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide and material with carbon element is 60～99.5:0.5～40.
Typically, in described lithium ion/lithium metal accumulation layer, the content of material with carbon element is 0.5～20%, it is preferred to 0.5～10%；And/or binder content is 2～50%, it is preferred to 10～20%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
Typically, in described lithium ion/lithium metal accumulation layer, the content of ceramic oxide is 30～97.5%, it is preferred to 30～80%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
The thickness of described lithium ion/lithium metal accumulation layer is 10～100 μm in the present invention.
Typically, the thickness of described lithium ion/lithium metal accumulation layer is preferably 50-100 μm, is more preferably 70-80 μm.
The particle diameter of described material with carbon element is 40nm～40 μm in the present invention.
Typically, the particle diameter of described material with carbon element is 100-1000nm, it is preferred to 400-600nm.
The particle diameter of described ceramic oxide is 10～100nm in the present invention.
Typically, the particle diameter of described ceramic oxide is 20-50nm, it is preferred to 30-40nm.
Should be understood that in negative material of the present invention, required material with carbon element, ceramic oxide, binding agent etc. have no particular limits, it is possible to select the material that this area is conventional, or prepare by conventional method, or be commercially available from market.
Electrolyte and preparation method thereof
Commercial electrolyte liquid comprises solvent and dissolves electrolytic salt in a solvent.Described preferred solvents ground is organic solvent, including (but being not limited to): Ethyl methyl carbonate (MethylEthylCarbonate), dimethyl carbonate (DimethylCarbonate), diethyl carbonate (DiethylCarbonate), ethylene carbonate (EthyleneCarbonate), Allyl carbonate (PropyleneCarbonate), fluorinated ethylene carbonate (Fluoroethylenecarbonate), 1, 2-dimethoxy-ethane, 1, 3 dioxolanes, methyl phenyl ethers anisole, acetas, propionic ester, butyrate, diethyl ether, acetonitrile, propionitrile.Described electrolytic salt includes cation, as used lithium (sodium) salt.Preferred lithium (sodium) salt includes lithium hexafluoro phosphate (sodium), lithium perchlorate (sodium), lithium chloride (sodium), lithium bromide (sodium) etc..Electrolyte solvent can be used alone, it is also possible to comprising two kinds or multi-solvents, electrolytic salt can be used alone, it is possible to comprises two kinds or multiple lithium (sodium) salt.
Electrolyte of the present invention prepares by adding appropriate film for additive in commercial electrolyte liquid.
Can accelerate to form the polymer passivation layer with protective effect at electrode surface by adding film for additive in commercial electrolyte liquid.
In the present invention described film for additive content in the electrolytic solution be 1～300 mmoles/liter, it is preferred to 1～50 mmoles/liter.
Typically, described film for additive includes (but being not limited to): isocyanates additive, carbonate ester additive, fluoro-ether additive or its combination.
In a preference, described isocyanates additive is hexamethylene diisocyanate (HDI).
Typically, described electrolyte is add the electrolyte that hexamethylene diisocyanate (HDI) additive is formed in conventional electrolysis liquid 3011R.
Commercial electrolyte liquid of the present invention and film for additive have no particular limits, and prepared by using conventional procedures, or be commercially available in market.
Lithium battery
Described lithium battery includes positive pole, negative pole, barrier film, electrolyte and shell in the present invention; described negative pole contains following negative material or is made up of following negative material; described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side; wherein; described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent; described electrolyte contains film for additive, and described film for additive forms polymer interface protective layer on lithium ion/lithium metal accumulation layer.
In a preference, described ceramic oxide is selected from lower group: Al2O3、ZrO2、SiO2, or its combination.
In a preference, described material with carbon element is selected from lower group: carbon black, graphite, charcoal granule, carbon nanotube, Graphene or its combination.
In a preference, described material with carbon element is special close high connductivity carbon black (Super-P).
In a preference, described binding agent is selected from lower group: tertiary benzene butyl rubber, polyimides, polyacrylate, sodium alginate or its combination.
In a preference, described supporting construction is selected from lower group: Copper Foil, copper mesh, lithium paper tinsel, nickel screen.
In described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide, material with carbon element and binding agent three is 30～97.5:0.5～20:2～50 in the present invention.
Specifically, in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide and material with carbon element is 60～99.5:0.5～40.
Typically, in described lithium ion/lithium metal accumulation layer, the content of material with carbon element is 0.5～20%, it is preferred to 0.5～10%；And/or binder content is 2～50%, it is preferred to 10～20%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
Typically, in described lithium ion/lithium metal accumulation layer, the content of ceramic oxide is 30～97.5%, it is preferred to 30～80%, by the gross weight gauge of lithium ion/lithium metal accumulation layer.
In the present invention described film for additive content in the electrolytic solution be 1～300 mmoles/liter, it is preferred to 1～50 mmoles/liter.
In a preference, described film for additive is selected from lower group: isocyanates additive, carbonate ester additive, fluoro-ether additive or its combination.
In a preference, described isocyanates additive is hexamethylene diisocyanate (HDI).
The thickness of described lithium ion/lithium metal accumulation layer is 10～100 μm in the present invention.
In a preference, the thickness of described lithium ion/lithium metal accumulation layer is preferably 50-100 μm, is more preferably 70-80 μm.
In a preference, the thickness of described polymer interface protective layer is 1～10nm, is more preferably 4-6nm.
The particle diameter of described material with carbon element is 40nm～40 μm in the present invention.
Typically, the particle diameter of described material with carbon element is 100-1000nm, it is preferred to 400-600nm.
The particle diameter of described ceramic oxide is 10～100nm in the present invention.
Specifically, the particle diameter of described ceramic oxide is 20-50nm, it is preferred to 30-40nm.
Specifically, described supporting construction is lithium sheet.
After described lithium battery circulates 22 weeks in the present invention, negative terminal surface is formed without obvious dendrite, and the interface impedance of described lithium battery is lower than the lithium battery or partly have without the specific negative material of the present invention and/or specific electrolyte.
In lithium battery of the present invention, except negative material of the present invention and electrolyte, other materials includes positive electrode, barrier film, conductive agent and binding agent etc. and has no particular limits, it is possible to carry out selecting the existing material in this area with reference to state of the art.
Typically, the barrier film of described battery can be the existing battery diaphragm in any this area, such as PP film, PE film, PP/PE/PP film, Teflon septum, ceramic porous membrane, fibreglass diaphragm etc..
Typically, described positive electrode can include one or more lithium metal oxides, such as the oxide of the metals such as manganese (Mn), ferrum (Fe), cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr).Described positive electrode active materials can also include one or more metal-oxide and metal sulfides etc..Such as (including, but are not limited to): LiMnO2, LiMn2O4, LiCoO2, Li2CrO7, LiNiO2, LiFeO2, LiNixCo1-XO2(0 < x < 1), LiFePO4, LiMnzNi1-ZO2(0<x<1；LiMn0.5Ni0.5O2), LiMn0.33Co0.33Ni0.33O2, LiMc0.5Mn1.5O4, wherein, Mc is a divalent metal；LiNixCoyMezO2, wherein Me represents a kind of or several element in Al, Mg, Ti, B, Ga, Si, x > 0；Y, z < 1.It addition, described positive electrode active materials may also comprise transition metal oxide, such as MnO2、V2O5；Transient metal sulfide, such as FeS2、MoS2、TiS2.Wherein, lithium ion transition metal oxide obtains more application, including: LiMn2O4, LiCoO2, LiNi0.8Co0.15Al0.05O2, LiFePO4And LiNi0.33Mn0.33Co0.33O2。
In a preference, described positive electrode is porous carbon back positive pole.
In a preference, described positive electrode is sulfur/carbon composite.
In a preference, described battery also has shell.
Described shell is not particularly limited, it is possible to be metal material or other composites etc..
Lithium battery preparation method
The preparation method of lithium battery of the present invention, including step:
(a-1) positive pole, negative pole, barrier film, electrolyte and shell are provided；
Wherein, described negative pole contains following negative material or is made up of following negative material; described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side; described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent; containing film for additive in described electrolyte, and described film for additive forms polymer interface protective layer on described lithium ion/lithium metal accumulation layer；
(a-2) described positive pole, negative pole, barrier film, electrolyte and shell are assembled the lithium battery described in being formed.
In a preference, described in be assembled under inert gas shielding to carry out.
Wherein, the preparation process of described negative material is as follows:
(b-1) binding agent is dissolved in advance in organic solvent and obtains binder solution；
(b-2) material with carbon element, ceramic oxide and binder solution are mixed in organic solvent acquisition negative material slurry；
(b-3) negative material slurry being coated on supporting construction one side, baking forms the negative pole with lithium ion/lithium metal accumulation layer.
Typically, described organic solvent includes (but being not limited to): N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO).
Typically, described organic solvent is N-Methyl pyrrolidone (NMP).
Specifically, described step (b-1) and/or (b-2) carry out under stirring.
Typically, described stirring is magnetic agitation.
In a preference, in described step (b-1) and/or (b-2), the time of stirring is 0.1～5 hour, it is preferred to 1～3 hour.
In a preference, described baking carries out under vacuum environment or inert gas shielding.
In a preference, described baking temperature is 80～140 DEG C, is more preferably 100～120 DEG C；Baking time is 0.5～20h, is more preferably 3～15h.
In a preference, described electrolyte is under inert gas shielding, is added in commercial electrolyte liquid by described film for additive and obtains.
Compared with prior art, lithium battery of the present invention prepared by negative material of the present invention is used to have following major advantage:
(1) excellent lithium metal storage function；
(2) lithium metallic dendrite can be effectively suppressed to grow；
(3) electrode interface uniform current density is made to be distributed；
(4) the low interface impedance of electrode surface is maintained.
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.The disclosed all features of this case description can with any composition forms use, each feature disclosed in description, it is possible to any alternative characteristics being provided identical, impartial or similar purpose replaces.Therefore except having special instruction, disclosed feature to be only impartial or similar features general example.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.
Unless otherwise defined, the same meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words.Additionally, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that preferably implementation described in literary composition and material only present a demonstration.
Embodiment 1
The preparation of Copper Foil battery 1
A, the polyimides that mass ratio is 10% is dissolved in N-Methyl pyrrolidone (NMP) solvent in advance, mixed stirring 3 hours in magnetic stirring apparatus, it is thus achieved that uniform sizing material；
B, it is 1:79:20 material with carbon element special close high connductivity carbon black (Super-P), Al in mass ratio2O3Powder and polyimides, add solvent N-methyl pyrilidone (NMP) in the mixture and be placed in magnetic stirring apparatus to mix stirring 3 hours, it is thus achieved that uniform sizing material.
C, the slurry in step b is coated uniformly on copper foil surface, toasts 12 hours with 120 DEG C in vacuum environment, be cut into disk that diameter is 16mm after natural cooling as the cathode pole piece with lithium ion/lithium metal accumulation layer.
D, by hexamethylene diisocyanate (HDI) by 20 mmoles/liter content add electrolyte, be sufficiently mixed uniformly.
E, by LiFePO4 (LiFePO4), Kynoar (PVdF) and the close high connductivity carbon black (Super-P) of spy prepare positive electrode slurry by powder quality than 8:1:1 Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) solution, it is then coated with tabletting on aluminium foil, vacuum drying 12h in vacuum drying oven, and it is cut into disk that diameter is 14mm as anode pole piece.
F, by d obtain the electrolyte with additive enter in polyethylene diagrams 20 microns thick by the minim of 70 μ L, and load CR2032 type button cell shell together with the anode pole piece obtained in the cathode pole piece obtained in c and e, put into the assembling of the glove box containing noble gas and obtain Copper Foil battery 1.
Result
Under the multiplying power that size of current is 0.5C, prepared Copper Foil battery 1 is carried out charge-discharge test.
The voltage curve of test gained is shown in Fig. 2, is wherein followed successively by 1-25 week from right to left, and as can be seen from Figure 2 except the efficiency for charge-discharge of first week is except 71%, the 2nd efficiency of thoughtful 15 weeks maintains essentially in about 92%.Capacity begins lower than 10mAh/g after maintaining 22 weeks.
Negative terminal surface Electronic Speculum figure before and after circulation is shown in Fig. 8, and before and after circulation, negative terminal surface grows without obvious dendritic crystalline lithium as can be seen from Figure 8.
Embodiment 2-12
The preparation of Copper Foil battery 2-12
Repeating embodiment 1, difference is in that: C: ceramic oxide: the content of binding agent mass ratio and film for additive is as shown in table 1.
C in table 1 embodiment 1-12: ceramic oxide: the content of binding agent mass ratio and film for additive
| Embodiment | C: ceramic oxide: binding agent mass ratio | Film for additive content (mmoles/liter) |
| 1 | 1:79:20 | 20 |
| 2 | 1:79:20 | 5 |
| 3 | 1:79:20 | 10 |
| 4 | 1:7:2 | 5 |
| 5 | 1:7:2 | 10 |
| 6 | 1:7:2 | 20 |
| 7 | 15:65:20 | 5 |
| 8 | 15:65:20 | 10 |
| 9 | 15:65:20 | 20 |
| 10 | 2:6:2 | 5 |
| 11 | 2:6:2 | 10 |
| 12 | 2:6:2 | 20 |
Comparative example 1
The preparation of the Copper Foil battery C1 without lithium ion/lithium metal accumulation layer
A, Copper Foil is cut into disk that diameter is 16mm as cathode pole piece.
B, by hexamethylene diisocyanate (HDI) by 20 mmoles/liter content add electrolyte, be sufficiently mixed uniformly.
C, by LiFePO4 (LiFePO4), Kynoar (PVdF) and the close high connductivity carbon black (Super-P) of spy prepare positive electrode slurry by powder quality than 8:1:1 Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) solution, it is then coated with tabletting on aluminium foil, vacuum drying 12h in vacuum drying oven, and it is cut into disk that diameter is 14mm as anode pole piece.
D, the electrolyte with additive obtained in b is entered in polyethylene diagrams 20 microns thick by the minim of 70 μ L, and and put into, together with the anode pole piece that obtains in the cathode pole piece that obtains in a and c, the Copper Foil battery C1 that the glove box assembling containing noble gas obtains without lithium ion/lithium metal accumulation layer.
Result
Under the multiplying power that size of current is 0.5C, prepared Copper Foil battery C1 is carried out charge-discharge test.
The voltage curve of test gained is shown in Fig. 3, is wherein followed successively by from right to left the 10th week, as can be seen from Figure 3 except the efficiency for charge-discharge of first week is except 54%, the 2nd thoughtful 10 weeks capacity attenuation comparatively fast, within the 7th week, capacity is lower than 10mAh/g.The 2nd efficiency meansigma methods of thoughtful 7 weeks is about 68%.
Comparative example 2
The preparation of Copper Foil battery C2 without film for additive in electrolyte
A, the polyimides that mass ratio is 10% is dissolved in N-Methyl pyrrolidone (NMP) solvent in advance, mixed stirring 3 hours in magnetic stirring apparatus, it is thus achieved that uniform sizing material；
B, by powder quality ratio for 1:79:20 material with carbon element special close high connductivity carbon black (Super-P), Al2O3Powder and polyimides, add solvent N-methyl pyrilidone (NMP) in the mixture and be placed in magnetic stirring apparatus to mix stirring 3 hours, it is thus achieved that uniform sizing material.
C, the slurry in step b is coated uniformly on copper foil surface, toasts 12 hours with 120 DEG C in vacuum environment, be cut into disk that diameter is 16mm after natural cooling as the cathode pole piece with lithium ion/lithium metal accumulation layer.
D, by LiFePO4 (LiFePO4), Kynoar (PVdF) and the close high connductivity carbon black (Super-P) of spy prepare positive electrode slurry by powder quality than 8:1:1 Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) solution, it is then coated with tabletting on aluminium foil, vacuum drying 12h in vacuum drying oven, and it is cut into disk that diameter is 14mm as anode pole piece.
E, non-additive electrolyte is entered in polyethylene diagrams 20 microns thick by the minim of 70 μ L, and load CR2032 type button cell shell together with the anode pole piece obtained in the cathode pole piece obtained in c and d, put into the glove box containing noble gas and assemble the Copper Foil battery C2 obtained without additive.
Result
Under the multiplying power that size of current is 0.5C, prepared Copper Foil battery C2 is carried out charge-discharge test.
The voltage curve of test gained is shown in Fig. 4, is wherein followed successively by 1-10 week from right to left, and as can be seen from Figure 4 except the efficiency for charge-discharge of first week is except 73%, the 2nd thoughtful 5 weeks capacity are decayed in a large number, and within the 6th week, capacity is lower than 10mAh/g.The 2nd efficiency meansigma methods of thoughtful 6 weeks is about 60%.
Comparative example 3
Without the preparation of Copper Foil battery C3 without film for additive in lithium ion/lithium metal accumulation layer and electrolyte
A, Copper Foil is cut into disk that diameter is 16mm as cathode pole piece.
B, by LiFePO4 (LiFePO4), Kynoar (PVdF) and the close high connductivity carbon black (Super-P) of spy prepare positive electrode slurry by powder quality than 8:1:1 Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) solution, it is then coated with tabletting on aluminium foil, vacuum drying 12h in vacuum drying oven, and it is cut into disk that diameter is 14mm as anode pole piece.
C, non-additive electrolyte is entered in polyethylene diagrams 20 microns thick by the minim of 70 μ L, and put into the glove box containing noble gas together with the anode pole piece obtained in the cathode pole piece obtained in a and b and assemble the Copper Foil battery C3 obtained in without lithium ion/lithium metal accumulation layer and electrolyte without additive.
Result
Under the multiplying power that size of current is 0.5C, prepared Copper Foil battery C3 is carried out charge-discharge test.
The voltage curve of test gained is shown in Fig. 5, is wherein followed successively by 1-4 week from right to left, and Copper Foil battery C3 is capacity exhaust after circulating 2 weeks as can be seen from Figure 5.And the efficiency for charge-discharge of first week and second week is only 22.7% and 16.9%.
Negative terminal surface Electronic Speculum figure before and after circulation is shown in Fig. 9, from Fig. 9 this it appears that the dendritic crystalline lithium of circulation front and back negative terminal surface deposits and growth.
Comparative example 4
The preparation of the not Copper Foil battery C4 of carbonaceous material in lithium ion/lithium metal accumulation layer
A, the polyimides that mass ratio is 10% is dissolved in N-Methyl pyrrolidone (NMP) solvent in advance, mixed stirring 3 hours in magnetic stirring apparatus, it is thus achieved that uniform sizing material；
B, it is the Al of 80:20 in mass ratio2O3Powder and polyimides, add solvent N-methyl pyrilidone (NMP) in the mixture and be placed in magnetic stirring apparatus to mix stirring 3 hours, it is thus achieved that uniform sizing material.
C, the slurry in step b is coated uniformly on copper foil surface, toasts 12 hours with 120 DEG C in vacuum environment, be cut into disk that diameter is 16mm after natural cooling as the cathode pole piece with lithium ion/lithium metal accumulation layer.
D, by hexamethylene diisocyanate (HDI) by 20 mmoles/liter content add electrolyte, be sufficiently mixed uniformly.
E, by LiFePO4 (LiFePO4), Kynoar (PVdF) and the close high connductivity carbon black (Super-P) of spy prepare positive electrode slurry by powder quality than 8:1:1 Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) solution, it is then coated with tabletting on aluminium foil, vacuum drying 12h in vacuum drying oven, and it is cut into disk that diameter is 14mm as anode pole piece.
F, by d obtain the electrolyte with additive enter in polyethylene diagrams 20 microns thick by the minim of 70 μ L, and load CR2032 type button cell shell together with the anode pole piece obtained in the cathode pole piece obtained in c and e, put into the glove box containing noble gas and assemble the Copper Foil battery C4 obtaining not carbonaceous material in lithium ion/lithium metal accumulation layer.
Result
Under the multiplying power that size of current is 0.5C, prepared Copper Foil battery C4 is carried out charge-discharge test.
The voltage curve of test gained is shown in Fig. 6, is wherein followed successively by from right to left the 22nd week, and as can be seen from Figure 6 except the efficiency for charge-discharge of first week is except 66%, the 2nd efficiency of thoughtful 15 weeks maintains essentially in about 87%.Capacity begins lower than 10mAh/g after maintaining 19 weeks.
Table 2 part charge-discharge test result
| 1st week | 2nd week | 11st week | 22nd week | |
| Embodiment 1 | 71% | 91% | 92% | 80% |
| Embodiment 4 | 19% | 65% | 90% | 91% |
| Embodiment 5 | 18% | 52% | 87% | 88% |
| Embodiment 6 | 16% | 72% | 95% | 96% |
| Embodiment 7 | 24% | 77% | 92% | 90% |
| Embodiment 8 | 22% | 61% | 89% | 88% |
| Embodiment 9 | 20% | 85% | 97% | 96% |
| Embodiment 10 | 27% | 75% | 93% | 91% |
| Embodiment 11 | 25% | 60% | 90% | 89% |
| Embodiment 12 | 22% | 83% | 97% | 97% |
| Comparative example 1 | 54% | 61% | Circulation stops, efficiency distortion | Circulation stops, efficiency distortion |
| Comparative example 2 | 73% | 53% | Circulation stops, efficiency distortion | Circulation stops, efficiency distortion |
| Comparative example 3 | 22.7% | 16.9% | Circulation stops, efficiency distortion | Circulation stops, efficiency distortion |
| Comparative example 4 | 66% | 87% | 88% | Circulation stops, efficiency distortion |
Fig. 7 is shown in the interface impedance contrast of the Copper Foil battery of embodiment 1 and comparative example 1,2,3,4 preparation, and the interface impedance of Copper Foil battery 1 of the present invention is lower than Copper Foil battery C1, C2, C3, the C4 or partly have without negative material of the present invention and/or electrolyte as ise apparent from FIG. 7.
Meanwhile, circulating result with embodiment 1-12 and compare, the cycle life of comparative example 1,2,3,4 is significantly lower than embodiment 1-12, although before comparative example 4, the circulating effect of 10 weeks is better than some embodiment, but its long-term cycle life is still lower than embodiment 1-12.This shows that the lithium battery of the present invention using negative material provided by the invention to prepare has obvious lithium metal storage function; and can play the protective effect of lithium in storing process; the Li dendrite effectively suppressing negative terminal surface in charge and discharge process is formed, and reduces the interface impedance of negative material simultaneously.
The all documents mentioned in the present invention are incorporated as reference all in this application, are individually recited as reference such just as each section of document.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.
Claims (10)
1. a lithium battery; described lithium battery includes positive pole, negative pole, barrier film, electrolyte and shell; it is characterized in that; described negative pole contains following negative material or is made up of following negative material; described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side; wherein; described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent; described electrolyte contains film for additive, and described film for additive forms polymer interface protective layer on lithium ion/lithium metal accumulation layer.
2. lithium battery as claimed in claim 1, it is characterised in that in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide, material with carbon element and binding agent three is 30～97.5:0.5～20:2～50.
3. lithium battery as claimed in claim 1, it is characterised in that in described lithium ion/lithium metal accumulation layer, the weight ratio of ceramic oxide and material with carbon element is 60～99.5:0.5～40.
4. lithium battery as claimed in claim 1, it is characterised in that described film for additive content in the electrolytic solution be 1～300 mmoles/liter, it is preferred to 1～50 mmoles/liter.
5. lithium battery as claimed in claim 1, it is characterised in that the thickness of described lithium ion/lithium metal accumulation layer is 10～100 μm.
6. lithium battery as claimed in claim 1, it is characterised in that the particle diameter of described material with carbon element is 40nm～40 μm.
7. lithium battery as claimed in claim 1, it is characterised in that the particle diameter of described ceramic oxide is 10～100nm.
8. lithium battery as claimed in claim 1, it is characterised in that described supporting construction is lithium sheet.
9. the preparation method of the lithium battery described in a claim 1, it is characterised in that include step:
(a-1) positive pole, negative pole, barrier film, electrolyte and shell are provided；
Wherein, described negative pole contains following negative material or is made up of following negative material; described negative material includes supporting construction and is coated on the lithium ion/lithium metal accumulation layer of described supporting construction one side; described lithium ion/lithium metal accumulation layer contains ceramic oxide, material with carbon element and binding agent; containing film for additive in described electrolyte, and described film for additive forms polymer interface protective layer on described lithium ion/lithium metal accumulation layer；
(a-2) described positive pole, negative pole, barrier film, electrolyte and shell are assembled the lithium battery formed described in claim 1.
10. preparation method as claimed in claim 9, it is characterised in that the preparation process of described negative material is as follows:
(b-1) binding agent is dissolved in advance in organic solvent and obtains binder solution；
(b-2) material with carbon element, ceramic oxide and binder solution are mixed in organic solvent acquisition negative material slurry；
(b-3) negative material slurry being coated on supporting construction one side, baking forms the negative pole with lithium ion/lithium metal accumulation layer.
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| CN111697270A (en) * | 2019-03-13 | 2020-09-22 | 北京师范大学 | Method for forming negative electrode protection layer through in-situ transfer |
| CN114678514A (en) * | 2017-01-09 | 2022-06-28 | 株式会社Lg化学 | Patterned lithium metal, electrode for secondary battery comprising same, and secondary battery |
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