CN108063222A - A kind of lithium ion battery negative material, its preparation method and lithium ion battery - Google Patents
A kind of lithium ion battery negative material, its preparation method and lithium ion battery Download PDFInfo
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- CN108063222A CN108063222A CN201710774888.8A CN201710774888A CN108063222A CN 108063222 A CN108063222 A CN 108063222A CN 201710774888 A CN201710774888 A CN 201710774888A CN 108063222 A CN108063222 A CN 108063222A
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- lithium
- lithium metal
- metal layer
- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 161
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 32
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000012546 transfer Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002845 discoloration Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910018537 Si SiOx Inorganic materials 0.000 claims description 5
- 229910008059 Si-SiOx Inorganic materials 0.000 claims description 5
- 229910006397 Si—SiOx Inorganic materials 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 74
- 238000004544 sputter deposition Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004062 sedimentation Methods 0.000 abstract description 6
- 238000005275 alloying Methods 0.000 abstract description 5
- 239000002210 silicon-based material Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 102
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 150000002641 lithium Chemical class 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910014913 LixSi Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910008062 Si-SiO2 Inorganic materials 0.000 description 4
- 229910006403 Si—SiO2 Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241001417527 Pempheridae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- -1 hexafluorophosphoric acid lithium salts Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical class [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Abstract
The present invention provides a kind of lithium ion battery negative material, including：Lithium metal layer；The Li-Si alloy layer being arranged on the lithium metal layer.Lithium ion battery negative material provided by the invention is in one layer of Li-Si alloy layer of lithium metal layer surface sputtering sedimentation, utilize the effect of alloying between lithium metal and silicon materials, an alloy-layer is formed on lithium metal surface, enable lithium ion evenly be deposited on cathode of lithium surface, so as to solve the problems, such as dendritic growth, lithium metal battery Xun Huan coulombic efficiency is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of lithium ion battery negative material, its preparation
Method and lithium ion battery.
Background technology
Lithium metal is very promising electrode material inside novel lithium battery system.The specific energy density of lithium metal
Up to 3860mAh/g is nearly 10 times of existing graphite cathode.The use of lithium an- ode, which can further expand, simultaneously currently may be used
With the anode material of lithium battery used.The positive electrode of tradition cooperation graphite cathode is needed containing elemental lithium, and using lithium metal
Cathode can be with extensive high-energy-density, and the positive electrode without elemental lithium matches (as vanadic anhydride, sulphur etc.).It is this kind of
The specific energy density of battery can reach 3-5 times of existing lithium ion battery.However, the extensive use of existing lithium an- ode is also deposited
In certain difficulty.Such as there is dendritic growth in lithium an- ode, it is low so as to cause lithium metal battery Xun Huan coulombic efficiency
Problem, it is to be resolved at present.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of lithium ion battery negative material, the present invention
The lithium ion battery negative material lithium metal battery Xun Huan coulomb of offer is efficient.
The present invention provides a kind of lithium ion battery negative material, including：
Lithium metal layer；
The Li-Si alloy layer being arranged on the lithium metal layer.Wherein, the ingredient of the Li-Si alloy layer is LixSi-SiOx, x
For 0~5 and be not 0.
Preferably, the thickness of the Li-Si alloy layer is 50~350nm.
The present invention provides a kind of preparation methods of lithium ion battery negative material, include the following steps：
A) lithium metal layer is provided；
B) by the way of magnetron sputtering by siliceous deposits on lithium metal layer, obtain deposition silicon lithium metal layer；
C the lithium metal layer for depositing silicon) is heated into melting, obtains lithium ion battery negative material.
Preferably, which is characterized in that
A) in the environment of low oxygen content, low water content, lithium metal layer is connected on base material；
B) global transfer is into Grown by Magnetron Sputtering room, under inert gas atmosphere, by silicon by the way of magnetron sputtering
It is deposited on lithium metal layer, obtains the lithium metal layer of deposition silicon；
C) for global transfer on plate, heating, lithiumation obtain lithium ion battery negative material.
Preferably, step B) global transfer into Grown by Magnetron Sputtering room, carries out vacuum pumping first, it then passes to lazy
Property gas, under inert gas atmosphere, by the way of magnetron sputtering by siliceous deposits on lithium metal layer, obtain deposition silicon lithium
Metal layer.
Preferably, step B) for global transfer into Grown by Magnetron Sputtering room, it is 1 × 10 to be evacuated to background pressure-7~3 ×
10-7Mbar is passed through inert gas, and it is 1 × 10 to make inert gas pressure-7,；The power of the magnetron sputtering is 50~70w；It is described
The time of magnetron sputtering is 2.0~4.0h.
Preferably, the operation for the connection of lithium metal layer being operated, being heated on base material melting carries out in glove box；
The H of the glove box2O<0.5~1ppm, O2<0.5~1ppm.
Preferably, the temperature of the heating melting is 250 DEG C~260 DEG C；The heating melts to discoloration as terminal；It is described
Discoloration is specially to become brown from yellow.
Preferably, the heating, which is melted on metallic plate, carries out；It is cooling after the heating melting；It is described to be cooled to nature
Cooling.
The present invention provides a kind of lithium ion batteries, and negative material is as the negative electrode of lithium ion battery described in above-mentioned technical proposal
The negative material that preparation method described in material or above-mentioned technical proposal is prepared is prepared.
The present invention also provides a kind of new-energy automobile, including the lithium ion battery described in above-mentioned technical proposal.
The present invention provides a kind of new-energy automobile, including the lithium ion battery described in above-mentioned technical proposal.
The present invention provides a kind of lithium ion battery negative material, including：Lithium metal layer；It is arranged on the lithium metal layer
Li-Si alloy layer.
Compared with prior art, the present invention provides a kind of lithium ion battery negative material, including：Lithium metal layer；It sets
Li-Si alloy layer on the lithium metal layer.Wherein, the ingredient of the Li-Si alloy layer is LixSi-SiOx, x is 0~5 and is not
0.Lithium ion battery negative material provided by the invention utilizes lithium gold in one layer of Li-Si alloy layer of lithium metal layer surface sputtering sedimentation
Belong to the effect of the alloying between silicon materials, an alloy-layer is formed on lithium metal surface so that lithium ion can be evenly is heavy
It accumulates on cathode of lithium surface, so as to solve the problems, such as dendritic growth, improves lithium metal battery cycle coulombic efficiency.
Description of the drawings
Fig. 1 is the structure diagram of negative electrode of lithium ion battery provided by the invention；
Fig. 2 is the result figure that the negative material that the present invention is prepared is taken pictures and scanned；
Fig. 3 is that lithium ion electrochemical deposits and dissolve out the Li prepared in original lithium paper tinsel and the embodiment of the present invention 2xSi-SiO2Change
Modification of surface morphology on property lithium paper tinsel；
Fig. 4 is the chemical property of modification lithium paper tinsel Symmetrical cells prepared by the embodiment of the present invention 3.(a) original Li paper tinsels are symmetrical
Battery (red) and the voltage distribution graph of modified lithium paper tinsel Symmetrical cells (blueness).
Specific embodiment
The present invention provides a kind of lithium ion battery negative material, including：
Lithium metal layer；
The Li-Si alloy layer being arranged on the lithium metal layer.Wherein, the Li-Si alloy layer is the film of the silicon containing lithiumation
Layer.Wherein, the ingredient of the Li-Si alloy layer is LixSi-SiOx, LixSi-SiOxIt is LixSi and SiOxMixture, x can be 0-
Number between 5, and be not 0 such as Li4.4Si。
Lithium ion battery negative material provided by the invention includes lithium metal layer.
The present invention is for the lithium metal layer without particular determination；It is well known to those skilled in the art；Can be
Lithium paper tinsel；It can be lithium piece.
The present invention is for the lithium metal layer thickness without particular determination, the known lithium ion battery of those skilled in the art
The thickness of negative material；It is preferred that it can be 10~1000 μm；More preferably 20~500 μm；Most preferably 30~100 μm.
Lithium ion battery negative material provided by the invention includes the Li-Si alloy layer being arranged on the lithium metal layer.
Li-Si alloy layer of the present invention is the layer comprising Li-Si alloy；Not just for Li-Si alloy；I.e.：Can be
The mixed coating of lithiumation silicon and silica；Or it is lithiumation silicon and the mixed coating of silicon；Or for lithiumation silicon and silica,
The mixed coating of silicon；Wherein, the autoxidation after silica here mostlys come from silicon in air, content may
Will not be very high, it is more difficult in concrete content experiment at present to determine.By current experiment condition, the silica imported is to cathode of lithium
It has no adverse effect.
The present invention provides a kind of negative electrode of lithium ion battery, including：
Lithium metal layer；
The Li-Si alloy layer being arranged on the lithium metal layer.
Negative electrode of lithium ion battery concrete structure of the present invention is as shown in Figure 1, wherein Fig. 1 is lithium ion provided by the invention
The structure diagram of battery cathode, wherein 1 is lithium metal layer, 2 be Li-Si alloy layer.
The Li-Si alloy layer of the present invention may be at micron order or nanometer grade thickness, this depends primarily upon technique and realizes item
Part or cost, though it is foreseeable that reduce the thickness of the thickness of Li-Si alloy layer, even lower than 50 nanometers, battery will be promoted
Efficiency.That is, when Li-Si alloy layer is arranged to nanoscale, its thickness is reduced, it will help promote the transmission of lithium ion
Efficiency, so as to promote battery efficiency, but corresponding Li-Si alloy layer thickness is lower, is less susceptible to holding Li-Si alloy layer itself
Integrality and relatively thin its physical strength of Li-Si alloy layer are also corresponding relatively low.If Li-Si alloy layer reaches micron order, that
This will reduce the transmission rate of lithium ion, increase electrode interface impedance, reduce the efficiency of battery.This programme is preferably arranged as
The Li-Si alloy layer of thin layer in the range of 50 nanometers to 350 nanometers, reduces the thickness of Li-Si alloy layer, will be obviously improved electricity
Pond efficiency, the mechanical strength of Li-Si alloy layer can be still in permissible range.
Wherein above-mentioned lithium metal layer and Li-Si alloy layer is above-mentioned has been clearly described, details are not described herein.
According to the present invention, the overall thickness of the Li-Si alloy layer is preferably 50~350nm；More preferably 60~330nm.
The preparation method of Li-Si alloy layer of the present invention is preferably specially：
By the way of magnetron sputtering by siliceous deposits on lithium metal layer, melting is reheated, is obtained.
The magnetron sputtering of the present invention and concrete mode of heating melting is following to be clearly described, it is no longer superfluous herein
It states.
According to the present invention, the thickness of the lithium metal layer is preferably 50~350nm；More preferably 60~330nm.
The discovery of the present inventor's creativeness in one layer of Li-Si alloy layer of lithium metal layer surface sputtering sedimentation, using lithium metal and
The effect of alloying between silicon materials forms an alloy-layer so that lithium ion can be evenly is deposited on lithium metal surface
Cathode of lithium surface, at the same it is more efficient by the final cycle coulomb of control of above-mentioned layer thickness.
The present invention provides a kind of preparation method of lithium ion battery negative material, including：
A) lithium metal layer is provided；
B) by the way of magnetron sputtering by siliceous deposits on lithium metal layer, obtain deposition silicon lithium metal layer；
C the lithium metal layer for depositing silicon) is heated into melting, obtains lithium ion battery negative material.
A kind of preparation method of lithium ion battery negative material provided by the invention provides lithium metal layer first.
The present invention is for the lithium metal layer without particular determination；It is well known to those skilled in the art；Can be
Lithium paper tinsel；It can be lithium piece.
The present invention is for the lithium metal layer thickness without particular determination, the known lithium ion battery of those skilled in the art
The thickness of negative material；It is preferred that it can be 10~1000 μm；More preferably 20~500 μm；Most preferably 30~100 μm.
According to the present invention, preferably lithium metal is placed on base material, is operated in glove box.
The present invention is for the base material without limiting；The base material of magnetron sputtering of the present invention is conductive material, general meeting
With metal base such as stainless steel substrates, copper sheet.
Base material well known to those skilled in the art with certain supportive and stability.The present invention is for the hand
Casing is without limiting；It is preferably in the glove box：H2O <0.5~1ppm, O2<0.5~1ppm.
A kind of preparation method of lithium ion battery negative material provided by the invention is sunk silicon by the way of magnetron sputtering
Product obtains the lithium metal layer of deposition silicon on lithium metal layer.
In the present invention, it is preferred to the lithium metal layer global transfer being placed on base material be into magnetron sputtering chamber, using silicon target
Carry out magnetron sputtering.
The present invention is for the magnetic control sputtering system without limiting；Preferably RF magnetic control sputtering systems；The model is excellent
Elect Oerlikon 350 as；Magnetron sputtering of the present invention preferably carries out at room temperature；As 25~35 DEG C.
Magnetron sputtering of the present invention carries out preferably under conditions of inert gas；More preferably in the item of single inert gas
It is carried out under part；The inert gas can be argon gas or nitrogen.
The scheme of replacement, magnetron sputtering are usually to be used for preparing inorganic oxide electrolyte or solar panel plated film
, the efficiency of its plated film is slow, and coating is very uniform.In order to realize similar coating effect, we can also use electrification
The method for learning redox plating silicon.
Preferably, global transfer is to being heated on plate, and this plate is preferably iron plate, it is of course also possible to select to make
With copper coin, nickel plate.
According to the present invention, the magnetic control sputtering system pump background pressure is preferably 1 × 10-7~3 × 10-7 mbar。
It introduces inert gas and so that the pressure of the magnetron sputtering is preferably 1 × 10-7mbar；The power of the magnetron sputtering
Preferably 50~70w；More preferably 60~70w；The time of the magnetron sputtering is preferably 2.0~4.0h；More preferably 3~
3.5h。
Silicon purity of the present invention is preferably 99.9%~99.99%.
The present invention for the silicon size without limit, disclosure satisfy that cathode requirement；Silicon of the present invention is excellent
Elect 2 inches as.
The present invention can also deposit silicon by the way of electrochemical redox.The present invention is for electrochemical redox
Concrete mode is without limiting；It is well known to those skilled in the art.
By siliceous deposits in lithium metal after, the lithium metal layer heating melting of silicon will be deposited, obtain lithium layer and Li-Si alloy
Composite bed；As lithium ion battery negative material.
It is preferred that it is specially：The lithium metal layer for depositing silicon is transferred in glove box, places heating melting on a metal plate, it is cold
But after, lithium ion battery negative material is obtained.
According to the present invention, the heating melting carries out preferably in glove box；The H of the glove box2O<0.5~1ppm,
O2<0.5~1ppm.
The temperature of the heating melting is preferably 250 DEG C~260 DEG C；More preferably 250 DEG C；The heating melts to discoloration
For terminal；The discoloration is specially to become brown from yellow.
After melting, lithium lithiumation that silicon is melted, surface color becomes brown from yellow；Form lithiumation silicon.LixSi.
In addition, the oxidation present invention additionally comprises such as silicon of side reaction slightly obtains silica.But content is extremely low, does not influence
Performance.
Heating of the present invention, which is melted on metallic plate, to be carried out；The metallic plate is preferably iron plate, copper coin or nickel plate；It is more excellent
Elect iron plate as.
It is cooling after heating melting of the present invention；It is described to be cooled to natural cooling.
The present invention is melted for the heating and the concrete operations mode of cooling is without limiting, and those skilled in the art are ripe
Know.
The present invention provides a kind of lithium ion battery negative material, including：Lithium metal layer；It is arranged on the lithium metal layer
Li-Si alloy layer.Lithium ion battery negative material provided by the invention is in one layer of Li-Si alloy of lithium metal layer surface sputtering sedimentation
Layer using the effect of alloying between lithium metal and silicon materials, forms an alloy-layer so that lithium ion energy on lithium metal surface
Evenly be deposited on cathode of lithium surface, so as to solve the problems, such as dendritic growth, improve lithium metal battery cycle coulombic efficiency.
The present invention provides a kind of lithium ion batteries, and negative material is as the negative electrode of lithium ion battery described in above-mentioned technical proposal
The negative material that preparation method described in material or above-mentioned technical proposal is prepared is prepared.
The lithium ion battery of the present invention can be used in various electrical equipments, such as 3C electronic equipments, unmanned plane and sweeper
The similar devices such as device people.This lithium battery can also be used for extensive energy storage, power grid energy storage.
Lithium ion battery negative material of the present invention is described in above-mentioned technical proposal, details are not described herein；Employ this
The negative material of invention solves the problems, such as dendritic growth, improves lithium metal battery Xun Huan coulombic efficiency.
The present invention is for positive electrode of the lithium ion battery etc. without limiting；Those skilled in the art are known i.e.
It can.
The present invention provides a kind of new-energy automobile, including the lithium ion battery described in above-mentioned technical proposal.
The present invention for the new-energy automobile remaining part without limit；As long as technical solution using the present invention
The lithium ion battery.
The lithium metal battery Xun Huan coulomb that new-energy automobile of the present invention uses is efficient.
Lithium ion battery negative material provided by the invention is in one layer of Li-Si alloy layer of lithium metal layer surface sputtering sedimentation, profit
With the effect of alloying between lithium metal and silicon materials, an alloy-layer is formed on lithium metal surface so that lithium ion can more
Even is deposited on cathode of lithium surface, so as to solve the problems, such as dendritic growth, improves lithium metal battery Xun Huan coulombic efficiency.
The metallic lithium layer of the present invention is the structure sheaf that cell electrochemical reaction occurs, and Li-Si alloy layer should can allow lithium
Ion passes through, so that electrochemical reaction is smoothed out.Li-Si alloy layer is more smooth, and Li-Si alloy layer changes the gold of script
Belong to the rough surface features of lithium layer.It is directly contacted directly avoiding problems lithium metal with electrolyte and electrochemistry circular response occurs
And gradually form dendrite.Protective layer causes lithium ion equably to deposit dissolution, so as to effectively prevent the growth of Li dendrite.And show
If have technology metallic lithium layer occur dendritic growth, in charge and discharge cycles repeatedly, dendritic growth can continue progress, performance
It is increasingly longer for dendrite, when dendrite touches anode through membrane hole, battery short circuit will be triggered, cause security incident.
Li-Si alloy layer primarily serves the penetrating effect of protection, ion, and Li-Si alloy layer has certain physical strength, can be effective
Dendritic growth process is prevented, and relatively thin Li-Si alloy layer can allow positive lithium ion quickly to pass through, that is to say, that lithium silicon
Alloy-layer can allow positive lithium ion is two-way to pass through, and thereby may be ensured that being smoothed out for discharge and recharge reaction, be obviously improved electricity
Cycle coulombic efficiency in pond.
In order to further illustrate the present invention, with reference to embodiments to lithium ion battery negative material provided by the invention and
Its preparation method is described in detail.
Embodiment 1
At room temperature, siliceous deposits is carried out in RF magnetic control sputtering systems (Oerlikon 350).Specifically preparation process is：In hand
(H in casing2O<0.5-1ppm, O2<0.5-1ppm) on the base material for being connected to lithium paper tinsel, then global transfer to magnetron sputtering system
In system growth room.System is pumped into background pressure to be adjusted to<1×10-7~3 × 10-7Then mbar introduces pure Ar gases to incite somebody to action
Operating pressure is maintained at 1 × 10-2mbar.By 2 inches of silicon (99.90~99.99% purity) target with 60W sputtering 3 it is small when.Growth
Afterwards, the Si lithium paper tinsels coated are transferred in glove box, are placed on the upper simultaneously 250 DEG C of heating meltings of iron plate.After fusing, what Si was melted
Lithium lithiumation, surface color become brown from yellow.After cooling, lithium ion battery negative material is obtained.
The negative material that the embodiment of the present invention 1 is prepared is taken pictures and scanned, the results are shown in Figure 2, and Fig. 2 is this
Invent the result figure that the negative material being prepared is taken pictures and scanned；In Fig. 2, (a) original Li paper tinsels；(b) given birth to by sputtering
The photo of long Si coatings lithium paper tinsel；(c) Li-Si alloy LixSi coats the photo of lithium paper tinsel；(d) sputtering growth Si surface profile with
Show thickness；The cross section of the SEM figures on (e, f) surface and the lithium paper tinsel of (g) Si coatings；(h, i) Si coating lithium paper tinsels cross section
EDX schemes, to reflect the signal of Si and O；Lithium surface topography after (j, k) coating cladding；(l,m)LixSi-SiO2Coating lithium paper tinsel
SEM sectional views (FIB cuts the cross section of LixSi coating lithium paper tinsels to show the thickness of coating).
The result shows that as shown in (a) (b) in Fig. 2, as surface deposits Si, the lithium paper tinsel yellowing of brilliant white.Heating is molten
After change, lithium lithiumation that the Si of face coat will be melted, color is with dimmed.As shown in figure (d), Si layers of face coat is about
330nm.Plan view (figure e, f) display sputtering growth Si nano particles of Si coating lithium paper tinsels equably cover the surface of lithium paper tinsel.From
Cross section (g) is seen, it can be seen that an apparent coating is red at the top of lithium paper tinsel.(figure h) is schemed according to EDS, Si and O signals all collect
In in the coating, the result is consistent with XPS analysis, and superficial layer is by Si and SiO2Composition.When molten lithium lithiumation, coating surface becomes
Obtain surface (figure j and k) that is more coarse, but still equably covering lithium paper tinsel.In cross it is observed that thickness about 350nm
Flat coating (m in Fig. 2).According to XPS research result, surface membrane component is lithiumation silicon (Lix) and SiO Si2Mixing
Object.
Embodiment 2
The experiment of electrode dissolution deposition is generally tested in button cell.Metal lithium electrode after modification dresses up Symmetrical cells
Do loop test.Used electrolyte is 1M hexafluorophosphoric acid lithium salts (LiPF6) and 1:1 ethylene carbonate (EC)/carbonic acid two
Ethyl ester (DEC) electrolyte mixes or 1M (trifyl) imide li (LiTFSI) is in capacity 1:1 1,3- dioxies penta
Ring (DOL)/1,2- dimethoxy-ethanes (DME) are mixed with the electrolyte of 1wt% lithium nitrates.The use of membrane is Celgard
2325(25μmPP/PE/PP).Reference frame as a comparison assembles naked lithium battery using the fresh Li paper tinsels scraped.Constant temperature is carried out to follow
Ring.Test equipment is used on 8 passage cell tester of 96 passage cell testers of Arbin or LAND.
At room temperature, siliceous deposits is carried out in RF magnetic control sputtering systems (Oerlikon 350).Specifically preparation process is：In hand
(H in casing2O<0.5-1ppm, O2<0.5-1ppm) on the base material for being connected to lithium paper tinsel, then global transfer to magnetron sputtering system
In system growth room.System is pumped into background pressure to be adjusted to<1×10-7~3 × 10-7Then mbar introduces pure Ar gases to incite somebody to action
Operating pressure is maintained at 1 × 10-2mbar.By 2 inches of silicon (99.90~99.99% purity) target with 50W sputtering 3.5 it is small when.It is raw
After length, the Si lithium paper tinsels coated are transferred in glove box, are placed on the upper simultaneously 250 DEG C of heating meltings of iron plate.After fusing, Si is melted
Lithium lithiumation, surface color becomes brown from yellow.After cooling, lithium ion battery negative material is obtained.
The negative material that the embodiment of the present invention 2 is prepared is dissolved out and deposited repeatedly；Dissolution and depositing current density are
1mA/cm2；Capacity is 1mAh/cm2.It is compared with existing simple lithium material, the results are shown in Figure 3, and Fig. 3 is lithium ion
The Li that electrochemical deposition and dissolution are prepared in original lithium paper tinsel and the embodiment of the present invention 2xSi-SiO2Surface topography on modified lithium paper tinsel
Variation.Wherein, when (a) third time deposition terminates, (b) third time is dissolved out with (c) the 7th deposition, the surface SEM figures of original lithium.
(d) the SEM image analysis of related active regions.The dissolution of (e, f) third time deposition (g, h) third time and (i, j) the 7th deposition
When, plan view and the amplification SEM image on original lithium surface.The dissolution of (k, l) third time disposal (m, n) third time and (o, p) the 7th
During secondary deposition, LixSi-SiO2The plan view on modified lithium paper tinsel surface and amplification SEM image.
The result shows that the sealer that the silicon coating of Grown by Magnetron Sputtering is formed in lithium metal can allow lithium metal more
Uniform deposition.EM figures can reflect that the surface topography of original and modified lithium paper tinsel has apparent difference in electrochemical process.When lithium sinks
Product observes many lithiums " island " when on the surface of original lithium paper tinsel on surface, surface utilisation is very low, is only 22.08%.From
After non-uniform surface removal lithium, apparent pit is formed, shows that lithium (accounts for the gross area from surface removal is uneven
14.63%).Even if after 7 Xun Huans, this non-uniform deposition and dissolved corrosion are still continuous.It turns out that
Surface area in electrochemical reaction there are still 35% is not engaged in reaction.Since real local current densities are very big
Used surface area is depended in degree, therefore this non-uniform deposition and dissolved corrosion may increase lithium in original lithium
Apply true local current densities on the surface during deposition and dissolution on paper tinsel, this is molten by the deposition for limiting high original lithium
Go out, and exacerbate the growth of Li dendrite.SEM enlarged drawings show that lithium " island " is assembled by loose Li dendrite and are formed (e, f)；Molten
In the case of going out, the lithium of deposition cannot remove completely, and typical lithium deposition is observed in pit.Due to loose with body lithium paper tinsel
Dynamic electrical contact, these remaining lithiums cannot be by further removals (g, h).In further deposition, more lithiums are plated in pit
On.By several cycles, lithium ion " trend " that Li dendrite is formed tend to merge into original lithium surface covering some are big more
Empty fluffy lithium plate.On the contrary, deposition and dissolution of the lithium on modified lithium paper tinsel are carried out by uniform mode.In sedimentation state
Under (k, l), apparent Li dendrite is not observed in coating surface；In the case of dissolution, also it is not observed on the surface
Pit.In this respect, the deposition of lithium and dissolution should be happened at below face coat region, and ionic conduction coating can be
Uniform lithium ion flux is provided in electrochemical process during the deposition of lithium and dissolution.Compared with the situation of original lithium paper tinsel, lithium
Uniform deposition and dissolution can effectively reduce and apply actual local current densities on the surface.
Embodiment 3
At room temperature, siliceous deposits is carried out in RF magnetic control sputtering systems (Oerlikon 350).Specifically preparation process is：In hand
(H in casing2O<0.5-1Ppm, O2<0.5-1Ppm) on the base material for being connected to lithium paper tinsel, then global transfer to magnetic control sputtering system
In growth room.System is pumped into background pressure to be adjusted to<1×10-7~3 × 10-7Then mbar introduces pure Ar gases with by work
1 × 10 is maintained at as pressure-2mbar.By 2 inches of silicon (99.90~99.99% purity) target with 70W sputtering 2.5 it is small when.Growth
Afterwards, the Si lithium paper tinsels coated are transferred in glove box, are placed on the upper simultaneously 250 DEG C of heating meltings of iron plate.After fusing, what Si was melted
Lithium lithiumation, surface color become brown from yellow.After cooling, lithium ion battery negative material is obtained.
Chemical property measure is carried out to the negative material that the embodiment of the present invention 3 is prepared, the results are shown in Figure 4, Fig. 4
For the chemical property of modification lithium paper tinsel Symmetrical cells prepared by the embodiment of the present invention 3.(a) original Li paper tinsels Symmetrical cells (red) and
The voltage distribution graph of modified lithium paper tinsel Symmetrical cells (blueness), current density is respectively 1mA/cm2To 10mA/cm2。(b) 1mA/cm2, (c) 2mA/cm23mA/cm (d)2Under original Li paper tinsels Symmetrical cells (red) and LixIt is (blue that Si is modified lithium paper tinsel Symmetrical cells
Color) the original Li paper tinsels Symmetrical cells (red) of detailed voltage's distribiuting (e) and 1mA/cm2When LixSi-SiO2Modified lithium paper tinsel is symmetrically electric
The voltage distribution graph in pond (blueness), the current density for depositing dissolution are 1mAh/cm2。
The result shows that due to the local current densities of optimization, LixUnder different current densities, (a) is shown Si batteries
Better rate capacity and cyclical stability.B, c are such as schemed, shown in d, when current density is from 1mA/cm2When changing to 3mA, LixSi
The overpotential of battery is (1mA/cm 2) extremely(3mA/cm 2), than original under same current density
Lithium paper tinsel is much lower.Current density is 1mA/cm2Cyclical stability test further demonstrate should be as a result, as (e) is shown.
1mA/cm2When, LixSi-SiO2Battery shows to have by 200 Xun HuansThe low mistake with flat voltage platform
The stable circulation of current potential, and original Li paper tinsels battery 156 times cycle after by internal short-circuit.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of lithium ion battery negative material, which is characterized in that including：
Lithium metal layer；
The Li-Si alloy layer being arranged on the lithium metal layer, wherein, the ingredient of the Li-Si alloy layer is LixSi-SiOx, x 0
~5 and be 0.
2. negative material according to claim 1, which is characterized in that the thickness of the Li-Si alloy layer is 50~350nm.
3. a kind of preparation method of lithium ion battery negative material, which is characterized in that include the following steps：
A) lithium metal layer is provided；
B) by the way of magnetron sputtering by siliceous deposits on lithium metal layer, obtain deposition silicon lithium metal layer；
C the lithium metal layer for depositing silicon) is heated into melting, obtains lithium ion battery negative material.
4. preparation method according to claim 3, which is characterized in that
A) in the environment of low oxygen content, low water content, lithium metal layer is connected on base material；
B) global transfer is into Grown by Magnetron Sputtering room, under inert gas atmosphere, by siliceous deposits by the way of magnetron sputtering
On lithium metal layer, the lithium metal layer of deposition silicon is obtained；
C) for global transfer on plate, heating, lithiumation obtain lithium ion battery negative material.
5. preparation method according to claim 4, it is characterised in that：
Step B) global transfer into Grown by Magnetron Sputtering room, carries out vacuum pumping, then passes to inert gas, lazy first
Property gas atmosphere under, by the way of magnetron sputtering by siliceous deposits on lithium metal layer, obtain deposition silicon lithium metal layer.
6. preparation method according to claim 5, it is characterised in that：
Step B) for global transfer into Grown by Magnetron Sputtering room, it is 1 × 10 to be evacuated to background pressure-7~3 × 10-7Mbar is passed through
Inert gas, it is 1 × 10 to make inert gas pressure-7Bar,；The power of the magnetron sputtering is 50~70w；The magnetron sputtering
Time be 2.0~4.0h.
7. preparation method according to claim 3, which is characterized in that described to grasp the connection of lithium metal layer on base material
Make, the operation of heating melting carries out in glove box；The H of the glove box2O<0.5~1ppm, O2<0.5~1ppm.
8. preparation method according to claim 3, which is characterized in that the temperature of the heating melting is 250 DEG C~260
℃；The heating melts to discoloration as terminal；The discoloration is specially to become brown from yellow；The heating is melted in metallic plate
Upper progress；It is cooling after the heating melting；It is described to be cooled to natural cooling.
9. a kind of lithium ion battery, which is characterized in that negative material is as the lithium-ion electric described in claim 1~2 any one
The negative material that preparation method described in pond negative material or claim 3~8 any one is prepared is prepared.
10. a kind of new-energy automobile, which is characterized in that including the lithium ion battery described in claim 9.
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