CN108336302A - A kind of lithium battery anode structure combination and preparation method thereof, lithium battery electric core - Google Patents
A kind of lithium battery anode structure combination and preparation method thereof, lithium battery electric core Download PDFInfo
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- CN108336302A CN108336302A CN201711371023.3A CN201711371023A CN108336302A CN 108336302 A CN108336302 A CN 108336302A CN 201711371023 A CN201711371023 A CN 201711371023A CN 108336302 A CN108336302 A CN 108336302A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 97
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 32
- -1 lithium ion compound Chemical class 0.000 claims abstract description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910017574 La2/3-xLi3xTiO3 Inorganic materials 0.000 claims description 8
- 229910017575 La2/3−xLi3xTiO3 Inorganic materials 0.000 claims description 8
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 8
- 229910012305 LiPON Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910013418 LiNixCoyM1-x-yO2 Inorganic materials 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 230000003139 buffering effect Effects 0.000 claims description 3
- 230000002427 irreversible effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000010416 ion conductor Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 229910012820 LiCoO Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910020717 Li0.33La0.56TiO3 Inorganic materials 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011378 penetrating method Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 relates to technical field of lithium batteries more particularly to a kind of combination of lithium battery anode structure and preparation method thereof, lithium battery electric cores.A kind of combination of lithium battery anode structure, including anode structure and the buffer layer that is formed on the anode structure, the anode structure include plus plate current-collecting body and the anode layer that is formed on the plus plate current-collecting body.The buffer layer is formed on the anode layer, and the plus plate current-collecting body, anode layer and buffer stack are added and set.The anode layer includes lithium ion compound, and the buffer layer includes lithium ion compound.The buffer layer can effectively prevent electrolyte and anode structure is in direct contact, avoid the irreversible reaction of the micro HF and anode structure in electrolyte, inhibit collapsing for anode structure under high-voltage charging simultaneously, so that the reversible capacity of battery and cyclicity made of the anode structure get a promotion.
Description
【Technical field】
Combined the present invention relates to technical field of lithium batteries more particularly to a kind of lithium battery anode structure and preparation method thereof,
Lithium battery electric core.
【Background technology】
Since Sony Corporation's exploitation nineties in last century first generation commercialization lithium battery, since lithium battery has high-energy density
The advantages of with output services voltage, is widely used in digital electronic goods, electric vehicle and extensive energy storage etc..Positive material
Material is the important component of lithium battery, directly affects the parameters such as capacity, the cycle performance of lithium battery.Common positive electrode
There are LiFePO4, cobalt acid lithium, LiMn2O4, ternary material etc..In various positive electrodes, cobalt acid lithium (LiCoO2) due to its period
Stability is good, good reversibility, energy density is high, it is convenient to prepare, and is widely used in every field.Many researchers have found by carrying
High stopping potential can be obviously improved LiCoO2The capacity of battery, but under high voltages, LiCoO2Cathode material structure can occur
It is irreversible to collapse, so as to cause capacity rapid decay.There is document report positive electrode LiCoO at present2Surface carries out metal oxygen
Compound cladding can improve this problem.Such as it discloses work as LiCoO in the prior art2It is 200nm that pole piece, which sputters a layer thickness,
Mixed with 2%Al2O3ZnO film when, between 3.0V -4.5V carry out charge and discharge 150 enclose after its capacity retention be 90%,
And the LiCoO not dealt with2Battery capacity retention only has 46%.Oxide coating effectively prevents electrode material and electrolysis upright
Contact inhibits the phase transformation in electrode material charge and discharge process, enhances LiCoO under high voltage2The structural stability of material, makes
The reversible capacity and cycle performance of battery get a promotion.But the lithium-ion-conducting of metal oxide itself is poor, will reduce
LiCoO2Lithium ion transport rate between material and electrolyte, to influence the high rate performance of battery.In addition, lithium battery charge and discharge
In electric process, electrode surface can generate one layer of solid electrolyte interface film (SEI films), and main component is the compound of lithium, surely
Fixed SEI films can effectively prevent organic macromolecule and enter in electrode material structure to enhance electrode stability, to effectively improve electricity
The cycle performance in pond, but will also result in a part of lithium loss simultaneously, therefore, how generating stable SEI films will solve
LiCoO2The critical issue of the high performance such as cell high-capacity, high voltage, high-energy.
【Invention content】
For overcome current lithium battery anode structure be easy to happen it is irreversible collapse, cause lithium battery structure power capacity become
Low, the problem of charge and discharge cycles effect is deteriorated, the present invention provides a kind of lithium battery anode stable structure, and specific capacity is high, charge and discharge
Good lithium battery anode structure combination of circulating effect and preparation method thereof, lithium battery electric core.
In order to solve the above-mentioned technical problem the present invention, provides a technical solution：
A kind of lithium battery anode structure combination, including anode structure and the buffer layer being formed on the anode structure, institute
It includes plus plate current-collecting body and the anode layer that is formed on the plus plate current-collecting body to state anode structure.The buffer layer is formed in described
On anode layer, and the plus plate current-collecting body, anode layer and buffer stack are added and are set.The anode layer includes lithium ion chemical combination
Object, the buffer layer include lithium ion compound.
Preferably, the lithium ion compound of the buffer layer includes fast-ionic conductor, and the fast-ionic conductor is specially
Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr, Hf
Deng), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
Preferably, the thickness of the buffer layer is 5-20nm.
Preferably, the anode structure layer includes plus plate current-collecting body layer and the anode that is formed on plus plate current-collecting body layer
Layer, the anode layer are cobalt acid lithium (LiCoO2)、LiNixCoyM1-x-yO2(0≤x ＜ 1,0≤y ＜ 1 and 0≤x+y≤1, M=Al,
Any one of Mn etc.).
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：
A method of preparing lithium battery structure combination：The plus plate current-collecting body for being formed with anode layer is provided, then in anode
The buffer layer is formed using physical vaporous deposition far from plus plate current-collecting body side on layer, the buffer layer includes lithium ion
Close object.
Preferably, the lithium ion compound includes Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y
≤ 2, A=Al, Ga, In, Sc, Y；M=Ge, Zr, Hf etc.), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、
LiPON、Li2CO3Any one of.
Preferably, method of the buffer layer deposition in the anode layer is specially magnetron sputtering method, and the magnetic control splashes
The step of penetrating method be specially：
The plus plate current-collecting body for being formed with anode layer is provided as substrate；
Buffer layer target is installed；
Vacuum is extracted into 5 X 10-4Pa or less；
The temperature of substrate frame is heated to 50-120 DEG C；
Adjusting air pressure is the ratio 7 of 0.5-1.5Pa, argon gas and oxygen:3-9:1, sputtering power is：80-120W is splashed
It penetrates.
Preferably, the air pressure is 1Pa, and the ratio of argon gas and oxygen is：7：3, sputtering power 100W.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of lithium battery electric core comprising above-mentioned
The lithium battery anode structure combination, negative pole structure and electrolyte, the negative pole structure combine phase with the anode structure
To setting, the electrolyte is located between anode structure combination and negative pole structure, and the buffer layer is contacted with the electrolyte.
Compared with the existing technology, the lithium battery anode structure combination includes anode structure and is formed in the anode structure
On buffer layer, the anode structure includes plus plate current-collecting body and the anode layer that is formed on the plus plate current-collecting body.It is described slow
It rushes layer to be formed on the anode layer, and the plus plate current-collecting body, anode layer and buffer stack are added and set.The anode layer packet
Lithium ion compound is included, the buffer layer includes lithium ion compound.It is formed with buffer layer on the anode structure, is avoided just
Pole structure is in direct contact with electrolyte, effectively electrolyte and anode structure is prevented to be in direct contact, is avoided the micro HF in electrolyte
With the irreversible reaction of anode structure, while inhibiting collapsing for anode structure under high-voltage charging, so that utilizing anode knot
The reversible capacity and cyclicity for the battery being configured to get a promotion.
The lithium ion compound of the buffer layer is a kind of in fast-ionic conductor, and fast-ionic conductor has at a certain temperature
Ionic conductivity that can be comparable with liquid electrolyte and low ionic conductance activation energy, preferably ensure electrolyte in conduction from
Electric conductivity between son and anode structure.
The thickness of the buffer layer, which is 5-20nm, to separate electrolyte and anode structure, while also can guarantee electrolyte
The conductive performance of middle conductive ion and anode structure.
The anode layer is cobalt acid lithium (LiCoO2)、LiNixCoyM1-x-yO2(0≤x ＜ 1,0≤y ＜ 1 and 0≤x+y≤1, M
Any one of=Al, Mn etc.).Cobalt acid lithium (LiCoO2) and LiNixCoyM1-x-yO2Stability of period it is good, good reversibility, energy
Metric density is high, can be used as the anode layer of the plus plate current-collecting body layer well.
Including the use of physical vaporous deposition by the buffer layer deposition on the anode structure, the lithium of the buffer layer
Ionic compound is specially Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc,
Y, M=Ge, Zr, Hf etc.), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
The buffer layer is formed on the anode structure layer using physical vaporous deposition, finer and close buffering can be obtained
Layer.
The air pressure is preferably 1.0Pa, and the ratio of argon gas and oxygen is preferably 7:3, sputtering power is preferably：100W makes
The buffer layer formed, which must be sputtered, has preferable compactness.
The third object of the present invention provides a kind of lithium battery electric core comprising lithium battery anode structure group described above
It closes, negative pole structure and electrolyte, the negative pole structure is oppositely arranged with anode structure combination, and the electrolyte is located at just
Between pole structure combination and negative pole structure, the buffer layer is contacted with the electrolyte.Buffer layer avoids anode structure well
It is in direct contact with electrolyte, avoids the irreversible reaction of the micro HF and anode structure in electrolyte, while inhibiting high-voltage charging
Lower anode structure collapses, so that being obtained using the reversible capacity of lithium battery electric core and cyclicity made of the anode structure
It is promoted.
【Description of the drawings】
Fig. 1 is the overall structure diagram of the lithium battery anode structure combination in the present invention；
Fig. 2 is the flow chart that the combination of lithium battery anode structure is prepared in the present invention
Fig. 3 is the electric core structure of lithium battery schematic diagram that buffer layer is formed in the present invention；
Fig. 4 is the electric core structure of lithium battery schematic diagram for not forming buffer layer in the present invention；
Fig. 5 is the discharge-rate performance test for the lithium battery structure for not forming buffer layer in the present invention and foring buffer layer
Figure；
Fig. 6 is that lithium battery structure does not form buffer layer and shape after high rate performance test after the 60th week in the present invention
At the AC impedance comparison diagram of the lithium battery electric core of buffer layer.
【Specific implementation mode】
It is with reference to the accompanying drawings and embodiments, right in order to make the purpose of the present invention, technical solution and advantage be more clearly understood
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Referring to Fig. 1, a kind of lithium battery anode structure combination 10, lithium battery anode structure combination 10 include anode structure
100 and the buffer layer 200 that is formed on the anode structure 100.The anode structure 100 includes plus plate current-collecting body 1001 and shape
At the anode layer 1002 on the plus plate current-collecting body 1001.The buffer layer 200 is formed on the anode layer 1002, and
The plus plate current-collecting body 1001, anode layer 1002 and buffer layer 200 are superposed.The anode layer 1002 includes lithium ion chemical combination
Object, the buffer layer 200 include lithium ion compound.
Collector refers to the structure or part for collecting electric current, metal foil, such as copper is generally referred on ion battery
Foil, aluminium foil, it may include lug to refer to.Its major function is that the electric current for generating cell active materials collects to be formed
Larger current versus output, therefore collector should come into full contact with active material, and as small as possible be preferred is answered in internal resistance.Afflux
Body is generally divided into plus plate current-collecting body and negative current collector, generally uses aluminium foil as plus plate current-collecting body, copper in lithium battery material
Foil is as negative current collector.Concrete reason is, aluminium is easy oxidation, is easy to form dense oxidation film on its surface and protects it from oxygen
Change, stable potential is high, is easy embedding lithium ion in the cathode of low potential, is unfit to do negative current collector.Copper meeting under high potential
Oxidation, is unfit to do plus plate current-collecting body.In the present invention, the plus plate current-collecting body 1001 used is aluminium foil.
The anode layer 1002 formed on plus plate current-collecting body layer 1001 includes lithium ion compound, the lithium ion compound
LiCoO selected from layer structure2(cobalt acid lithium), LiNixCoyM1-x-yO2(0<x≤1,0≤y<1 and 0<X+y≤1, M=Al, Mn)
Any one of.
Preferably, the lithium ion compound that anode layer 1001 includes mainly selects LiCoO2(cobalt acid lithium).Cobalt acid lithium
(LiCoO2) stability of period is good, good reversibility, energy density are high, it is convenient to prepare, be widely used in every field.Cobalt simultaneously
The chemical property of sour lithium is superior, and battery polarization, less fuel factor can be inhibited to improve high rate performance, can protect well well
Shield anode structure 100 is not corroded from an electrolyte.
Due to during liquid lithium battery first charge-discharge, electrode material (including anode structure layer and negative electrode material layer)
It reacts on solid-liquid phase interface with electrolyte, forms one layer of passivation layer for being covered in electrode material surface.This passivation layer
It is a kind of boundary layer, it is Li that the feature with solid electrolyte, which is electronic body,+Excellence conductor, Li+Can pass through should
Passivation layer is freely embedded and deviates from, therefore this layer of passivating film is referred to as " solid electrolyte interface film " (solid
Electrolyte interface) abbreviation SEI films.This layer of SEI film can effectively prevent macromolecular solvent from entering anode structure
In, there is good protective effect to anode structure, enhances cyclicity, but this process can cause the loss of lithium.In addition, traditional
Contain micro hydrofluoric acid (HF) in electrolyte, this is mainly due to the presence of traces of moisture in electrolyte, hydrofluoric acid (HF)
It can react with anode structure and SEI films, cause the unstable of SEI films；It is easy to cause anode structure simultaneously to be corroded, cause
It is collapsed.Therefore one layer of buffer layer 200 is formed on anode structure 100, as artificial SEI films.
In the present invention, buffer layer 200 include lithium ion compound, the lithium ion compound be fast-ionic conductor such as：
Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr, Hf
Deng), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
Preferably, the lithium ion compound that the buffer layer 200 includes is specially Li0.33La0.56TiO3。
Li0.33La0.56TiO3The solid electrolyte of solid electrolyte intermediate ion conductivity highest (1mS/cm), can effectively improve lithium from
The conduction velocity of son improves the electric conductivity of anode structure 100.
Buffer layer 200 can reduce the loss of lithium ion during charging cycle as artificial SEI films well, improve first
The coulomb effect of secondary charge and discharge improves energy density, while inhibiting bad pair between anode structure 100 and electrolyte contact interface
Reaction occurs, and effectively improves the stability of 100 structure of anode structure.Can also it inhibit in During high voltage charge simultaneously, due to lithium
Ion abjection causes collapsing for 100 structure of anode structure, enhances the stability of 100 structure of anode structure, improves the cycle of battery
Performance.In the present invention, 4.5V can be reached by foring the blanking voltage of anode structure 100 after buffer layer 200.
The second object of the present invention is to provide a kind of preparation method of lithium battery anode structure combination, including provides formation
There is the plus plate current-collecting body 1001 of anode layer 1002, then the side far from plus plate current-collecting body 1001 in anode layer 1002 utilizes object
Physical vapor deposition method forms the buffer layer 200, and the buffer layer 200 includes lithium ion compound.The lithium ion compound
Including Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr,
Hf etc.), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
Referring to Fig. 2, with Li in present embodiment0.33La0.56TiO3For illustrate.
In the present invention, described that the buffer layer 200 is deposited on the anode layer 1002 using physical vaporous deposition
On method be specially magnetron sputtering method, the step of magnetron sputtering method is specially：
S1：The plus plate current-collecting body for being formed with anode layer is provided as substrate；；
S2：Buffer layer target namely Li are installed0.33La0.56TiO3Target；
S3：Vacuum is extracted into 5 × 10-4Pa or less；
S4：The temperature of substrate frame is heated to 50-120 DEG C；
S5：Adjust that air pressure is 0.5-1.5Pa, the ratio of argon gas and oxygen is 7:3-9:1, sputtering power be 80-120W into
Row sputtering.
In step S5 described above, air pressure is preferably 1.0Pa, and the ratio of argon gas and oxygen is preferably：7:3, sputtering power
Preferably：100W.
After being finished by above-mentioned steps S5 sputterings, the thickness of obtained buffer layer 200 is 5-20nm, preferably
10nm。
Referring to Fig. 3, the third object of the present invention is to provide a kind of lithium battery electric core 20 comprising lithium described above
Battery cathode structure combination 10, negative pole structure 400 and electrolyte 300, the negative pole structure 400 are combined with the anode structure
10 are oppositely arranged, and the electrolyte 300 is located between anode structure combination 10 and negative pole structure 400, and the buffer layer 200 is with institute
State the contact of electrolyte 300.The anode structure 100 includes plus plate current-collecting body layer 1001 and is formed in the plus plate current-collecting body layer
Anode layer 1002 on 1001, the buffer layer 200 are formed in side of the anode layer 1002 towards electrolyte 300.It is described negative
Pole structure 400 includes negative current collector layer 4002 and is formed in the negative current collector layer 4002 towards 300 side of electrolyte
Negative film layer 4001.Using copper foil as negative current collector layer 4002, the anode layer 1002 and negative film in the present invention
Layer 4002 is oppositely arranged.
Incorporated by reference to Fig. 3 and Fig. 4, has to further verify the lithium battery electric core 20 provided in the present invention and preferably imitate
Fruit, the present invention also provides another lithium battery electric core 30, difference lies in institutes for the lithium battery electric core 30 and lithium battery electric core 20
It states in the lithium battery electric core 30 and buffer layer 200 is not formed between anode structure 100 and electrolyte layer 300.
Incorporated by reference to Fig. 3, Fig. 4 and Fig. 5, the abscissa of Fig. 5 is cycle-index, and ordinate is discharge capacity.In order to further
Lithium battery electric core 20 provided in the verification present invention has preferably effect, to the lithium battery electric core 20 and lithium battery electric core
30 under equal conditions carry out discharge-rate performance detection simultaneously.
When carrying out 2C electric discharges, the discharge capacity of lithium battery electric core 20 is about 70mAh/g, and the electric discharge of lithium battery electric core 30 is held
Amount is about 20mAh/g.It can be seen that the discharge capacity of the lithium battery electric core 20 after foring buffer layer 200 is apparently higher than and is not formed
The lithium battery electric core 30 of buffer layer 200.
In addition, the 0.2C charge-discharge tests of low range are carried out to the lithium battery electric core 20 after progress high rate charge-discharge,
The discharge capacity for being formed with the lithium battery electric core 20 of buffer layer 200 is maintained at 165mAh/g, and the lithium of buffer layer 200 is not formed
It is decaying that landslide, which occurs, in the discharge capacity of battery battery core 30.As it can be seen that the lithium battery electric core 30 after foring buffer layer 200 has
Higher stability.
It please join in conjunction with Fig. 6, the lithium battery electric core 20 after testing multiplying power and lithium battery electric core 30, be carried out at the same time exchange resistance
Anti- test (EIS) forms its resistance in electrolyte 300 of the lithium battery electric core 20 after buffer layer 200 and is tied in anode
The resistance at 100 interface of structure is below the lithium battery electric core 30 for not forming buffer layer 200, and forms after buffer layer 200 just
Pole structure 100 does not occur new interface.
Compared with the existing technology, the lithium battery anode structure combination includes anode structure and is formed in the anode structure
On buffer layer, the anode structure includes plus plate current-collecting body and the anode layer that is formed on the plus plate current-collecting body.It is described slow
It rushes layer to be formed on the anode layer, and the plus plate current-collecting body, anode layer and buffer stack are added and set.The anode layer packet
Lithium ion compound is included, the buffer layer includes lithium ion compound.It is formed with buffer layer on the anode structure, is avoided just
Pole structure is in direct contact with electrolyte, effectively electrolyte and anode structure is prevented to be in direct contact, is avoided the micro HF in electrolyte
With the irreversible reaction of anode structure, while inhibiting collapsing for anode structure under high-voltage charging, so that utilizing anode knot
The reversible capacity and cyclicity for the battery being configured to get a promotion.
The lithium ion compound of the buffer layer is a kind of in fast-ionic conductor, and fast-ionic conductor has at a certain temperature
Ionic conductivity that can be comparable with liquid electrolyte and low ionic conductance activation energy, preferably ensure electrolyte in conduction from
Electric conductivity between son and anode structure.
The thickness of the buffer layer, which is 5-20nm, to separate electrolyte and anode structure, while also can guarantee electrolyte
The conductive performance of middle conductive ion and anode structure.
The anode layer is cobalt acid lithium (LiCoO2)、LiNixCoyM1-x-yO2(0≤x ＜ 1,0≤y ＜ 1 and 0≤x+y≤1, M
Any one of=Al, Mn etc.).Cobalt acid lithium (LiCoO2) and LiNixCoyM1-x-yO2Stability of period it is good, good reversibility, energy
Metric density is high, can be used as the anode layer of the plus plate current-collecting body layer well.
Including the use of physical vaporous deposition by the buffer layer deposition on the anode structure, the lithium of the buffer layer
Ionic compound is specially Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc,
Y, M=Ge, Zr, Hf etc.), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
The buffer layer is formed on the anode structure layer using physical vaporous deposition, finer and close buffering can be obtained
Layer.
The air pressure is preferably 1.0Pa, and the ratio of argon gas and oxygen is preferably 7:3, sputtering power is preferably：100W makes
The buffer layer formed, which must be sputtered, has preferable compactness.
The third object of the present invention provides a kind of lithium battery electric core comprising lithium battery anode structure group described above
It closes, negative pole structure and electrolyte, the negative pole structure is oppositely arranged with anode structure combination, and the electrolyte is located at just
Between pole structure combination and negative pole structure, the buffer layer is contacted with the electrolyte.Buffer layer avoids anode structure well
It is in direct contact with electrolyte, avoids the irreversible reaction of the micro HF and anode structure in electrolyte, while inhibiting high-voltage charging
Lower anode structure collapses, so that being obtained using the reversible capacity of lithium battery electric core and cyclicity made of the anode structure
It is promoted.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention
Any modification made by within then, equivalent replacement and improvement etc. should all include within protection scope of the present invention.
Claims (10)
1. a kind of lithium battery anode structure combination, it is characterised in that：Including anode structure and it is formed on the anode structure
Buffer layer, the anode structure include plus plate current-collecting body and the anode layer that is formed on the plus plate current-collecting body, the buffer layer
It is formed on the anode layer, and the plus plate current-collecting body, anode layer and buffer stack are added and set, the anode layer includes lithium
Ionic compound, the buffer layer include lithium ion compound.
2. lithium battery anode structure combination as described in claim 1, it is characterised in that：The lithium ion compound of the buffer layer
Specially Li1+yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge,
Zr, Hf etc.), La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
3. lithium battery anode structure combination as described in claim 1, it is characterised in that：The thickness of the buffer layer is 5-
20nm。
4. lithium battery anode structure combination as described in claim 1, it is characterised in that：The anode layer includes cobalt acid lithium
(LiCoO2)、LiNixCoyM1-x-yO2Any one of (0≤x ＜ 1,0≤y ＜ 1 and 0≤x+y≤1, M=Al, Mn).
5. a kind of lithium battery electric core, it is characterised in that：It include the lithium battery anode structure as described in any one of claim 1-4
Combination.
6. lithium battery electric core as claimed in claim 5, it is characterised in that：Further include negative pole structure and electrolyte, it is described negative
Pole structure is oppositely arranged with anode structure combination, and the electrolyte is located between anode structure combination and negative pole structure, institute
Buffer layer is stated to contact with the electrolyte.
7. a kind of preparation method of lithium battery anode structure combination, it is characterised in that：Include the following steps：Offer is formed with anode
Then the plus plate current-collecting body of layer forms the buffering far from plus plate current-collecting body side in anode layer using physical vaporous deposition
Layer, the buffer layer includes lithium ion compound.
8. the preparation method of lithium battery anode structure combination as claimed in claim 7, the lithium ion compound includes Li1+ yAyTi2-x-yMx(PO4)3(0≤x≤2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr, Hf etc.),
La2/3-xLi3xTiO3(0.05 ＜ x ＜ 0.167), LiNbO3、LiPON、Li2CO3Any one of.
9. the preparation method of lithium battery anode structure combination as claimed in claim 7, it is characterised in that：The buffer layer deposition
The step of method in the anode layer is specially magnetron sputtering method, the magnetron sputtering method be specially：
The plus plate current-collecting body for being formed with anode layer is provided as substrate；
Buffer layer target is installed；
Vacuum is extracted into 5 X 10-4Pa or less；
The temperature of substrate frame is heated to 50-120 DEG C；
Adjusting air pressure is the ratio 7 of 0.5-1.5Pa, argon gas and oxygen:3-9:1, sputtering power is：80-120W is sputtered.
10. the preparation method of lithium battery anode structure combination as claimed in claim 9, it is characterised in that：Air pressure is preferably
The ratio of 1.0Pa, argon gas and oxygen is preferably：7:3, sputtering power is preferably：100W.
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