CN102683639B - A kind of anode sheet of lithium ion battery and use the lithium ion battery of this anode strip - Google Patents
A kind of anode sheet of lithium ion battery and use the lithium ion battery of this anode strip Download PDFInfo
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- CN102683639B CN102683639B CN201210191929.8A CN201210191929A CN102683639B CN 102683639 B CN102683639 B CN 102683639B CN 201210191929 A CN201210191929 A CN 201210191929A CN 102683639 B CN102683639 B CN 102683639B
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- lithium ion
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- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000013528 metallic particle Substances 0.000 claims abstract description 25
- 239000006183 anode active material Substances 0.000 claims abstract description 17
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 239000006258 conductive agent Substances 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims description 29
- 229910045601 alloy Inorganic materials 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910018540 Si C Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910001339 C alloy Inorganic materials 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052767 actinium Inorganic materials 0.000 claims description 2
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011884 anode binding agent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 239000007767 bonding agent Substances 0.000 abstract description 3
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 2
- 230000008034 disappearance Effects 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 13
- 230000002427 irreversible effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to technical field of lithium ion, particularly relate to a kind of anode sheet of lithium ion battery, comprise anode collector and the anode diaphragm being arranged at anode collector, anode diaphragm comprises anode active material, bonding agent and conductive agent, anode active material comprises silicon alloy, anode collector arranges porose, is filled with lithium metallic particles in hole.Relative to prior art, after adopting anode strip of the present invention to be made into battery, namely lithium metal particle the form of lithium ion can be embedded in anode active material and goes, in advance lithium ion is added in anode strip, thus can lithium ion loss effectively in battery initial charge process, improve the initial charge efficiency of battery; Meanwhile, the dissolving of lithium metallic particles and disappearance, make again collection anode fluid leave many holes, this some holes, by inner space when becoming expansion of anode sheet, namely can improve the expansion of anode strip effectively.In addition, the invention also discloses a kind of lithium ion battery comprising this anode strip.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of lithium ion battery and anode strip thereof.
Background technology
From existing market, mobile electronic terminal is lightening, panelized becomes trend with functional diversities.The rise of low-carbon economy, for lithium ion battery opens new market in the application in locomotive equipment field.They all propose common requirement to lithium ion battery: high-energy-density.But the energy density taking graphite as the lithium ion battery of anode, close to the limit, can not meet the demands gradually.There is the anode material of alloy material as a new generation of more high power capacity, be expected to replace graphite most and be applied in commercial lithium ion battery.Therefore, no matter be scientific research institutions, colleges and universities or each large enterprises, it is like a raging fire that the exploitation of alloy material lithium ion battery is carried out.
But, with prior art, alloy anode has the following disadvantages (being described for silicon alloy anode): one is high irreversible capacity, except the small amount irreversible capacity that formation solid electrolyte film (SEI film) must consume, more importantly due to the characteristic of material self, alloy anode is difficult to by the complete deintercalation of lithium of embedding out, and namely the lithium ion of part is trapped in inside, thus form irreversible capacity loss, many about 20% of irreversible capacity loss ratio graphite system.Thus, the advantage of the high-energy-density of alloy anode is just weakened widely.Two is huge volumetric expansions.Alloy material is after embedding lithium, and will become amorphous phase from crystalline phase, volume significantly increases.By the result of theory calculate, the later alloy volume of complete embedding lithium is by increase 3 times.Therefore, develop alloy anode system lithium ion battery must solve two problems: the irreversible capacity loss of compensator alloy anode architectures battery and improve alloy anode expansion.
From the loss of reduction irreversible capacity, directly improving anode material is best approach.But because the preparation of current alloy anode material is also not overripened, the method that improvement material reduces irreversible capacity loss does not also have effect.A kind of method often appeared in scientific and technical literature is also had to be compensate the irreversible lithium ion of silicon anode in charge and discharge process by adding lithium metal.Its general way sprinkles one deck lithium powder on the surface of anode strip, is then pressed in anode strip by lithium powder.This method can play the effect of supplementary irreversible capacity really.But also have some shortcomings: one, lithium powder is sprinkling upon the skewness on anode strip; The two, pole piece needs reroll, the process of reroll easily cause pole piece mesopore structure and distribution uncontrollable, and in lithium ion battery, the pore structure of pole piece is of crucial importance with distribution; Moreover the method cannot improve the expansion of anode strip, and then the expansion of battery cannot be improved.Therefore, when the lithium ion battery of suitability for industrialized production alloy anode system, the uncontrollable of these factors will make the consistency of battery performance be difficult to ensure.
In view of this, necessaryly provide a kind of and can compensate the irreversible capacity loss of battery adopting alloy anode, lithium ion battery and anode strip thereof that alloy anode expands can be improved again.
Summary of the invention
An object of the present invention is to provide a kind of irreversible capacity loss that can compensate the battery adopting alloy anode, the anode sheet of lithium ion battery that alloy anode expands can be improved again, with overcome alloy anode of the prior art be difficult to solve simultaneously compensate adopt the irreversible capacity loss of the battery of alloy anode and improve alloy anode expansion deficiency.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of anode sheet of lithium ion battery, comprise anode collector and the anode diaphragm being arranged at described anode collector, described anode diaphragm comprises anode active material, bonding agent and conductive agent, and described anode active material comprises Si-C alloy, Si
ao
bm
cand Si
ao
bm
cat least one in-C alloy, wherein a, b, c represents atomic percent respectively, 0≤a≤100,0≤b<100,0≤c<100, M is at least one in aluminium, silicon, tin, manganese, indium, yttrium, molybdenum, niobium, tantalum, iron, copper, titanium, chromium, nickel, cobalt, zirconium, lanthanum and actinium element, and described anode collector arranges porose, is filled with lithium metallic particles in described hole.
One as anode sheet of lithium ion battery of the present invention is improved, and the thickness of described anode collector is less than or equal to 40 μm.The thickness of anode collector is too large, can have considerable influence, and can make Kong Taishen, be unfavorable for the stripping of lithium metal particle to the energy density of battery.
One as anode sheet of lithium ion battery of the present invention is improved, and the gross area in described hole is less than or equal to 70% with the gross area ratio of described anode strip.If the gross area in hole is too large, the intensity of anode collector can be reduced, weaken its supporting role, and too little with the contact area of anode diaphragm, coming off of anode diaphragm can be caused, battery can not normally be used.
One as anode sheet of lithium ion battery of the present invention is improved, and the gross area in described hole and the gross area of described anode strip are than being 10-50%, and this is preferred scope.
One as anode sheet of lithium ion battery of the present invention is improved, and the gross area in described hole is 30% with the gross area ratio of described anode strip, and this is better selection.
One as anode sheet of lithium ion battery of the present invention is improved, and described hole is uniformly distributed in the plane of described anode collector, is conducive to the manufacture in hole, and can provide uniform expansion of anode sheet space for anode strip.
One as anode sheet of lithium ion battery of the present invention is improved, and the diameter in described hole is 0.01-10 μm.The diameter in hole is too large, is unfavorable for the filling of lithium metallic particles; The diameter in hole is too little, is unfavorable for the manufacture in hole, and easily makes lithium metallic particles broken.
One as anode sheet of lithium ion battery of the present invention is improved, the Surface coating of described lithium metallic particles has at least one in carbon, metal oxide, metal carbides and metal nitride, the existence of coating layer can avoid lithium metal to contact with the direct of air, thus ensures the activity of lithium metallic particles.
One as anode sheet of lithium ion battery of the present invention is improved, and the thickness of the coating layer of described lithium surface of metal particles is 30-300nm, and coating layer is too thick, is unfavorable for the stripping of lithium metallic particles; Coating layer is too thin, is not easy again to play good covered effect, lithium metal can not be avoided preferably to contact with the direct of air, thus lithium metallic particles is lost activity.
Relative to prior art, after adopting anode strip of the present invention to be made into battery, when battery does not charge, namely lithium metal particle the form of lithium ion can be embedded in anode active material and goes, in advance lithium ion is added in anode strip, these lithium ions supplemented in advance can reduce the lithium ion loss of cathode active material in battery initial charge process effectively, namely improve the initial charge efficiency of battery; Meanwhile, be filled in the dissolving of the lithium metallic particles in anode current collector body opening, disappearance, make again collection anode fluid leave many holes, this some holes, by inner space when becoming expansion of anode sheet, namely can improve the expansion of anode strip effectively.
Another object of the present invention is to provide a kind of lithium ion battery, the barrier film comprising cathode sheets, anode strip and be arranged between described cathode sheets and anode strip, and electrolyte, and described anode strip is anode sheet of lithium ion battery of the present invention.
Preferably, battery is not when charging, and the Lithium-ion embeding in lithium particle accounts for 1/3 or 1/6 of battery full charge capacity to the capacity in anode strip.
Relative to prior art, lithium ion battery of the present invention, owing to have employed above-mentioned anode strip, had therefore both had higher efficiency first, had had again less expansion, thus ensured the consistency of battery in size and chemical property.And due to adopt anode strip be alloy anode, therefore there is very high energy density, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the structural representation of the anode collector in anode strip of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
embodiment 1:be illustrated in figure 1 the structural representation of the anode collector 1 that anode strip of the present invention adopts.Anode collector 1 arranges porose 11, in hole 11, is filled with lithium metallic particles.Hole 11 in anode collector 1 can adopt the mode of mechanical punching to obtain, and also can be obtained by the mode of laser drilling.
Below, anode collector 1 selects Copper Foil.
The making of anode strip: using the Copper Foil of 9um as base material, copper foil base material is stamped array that aperture is the hole 11 of 1 μm equably, porose 11 the gross area account for 10% of whole anode strip area.Then be filled in hole 11 by the lithium metallic particles being coated with conductive carbon, the thickness of conductive carbon layer is 100nm, obtains anode collector 1 of the present invention.
Then Si oxide alloy (SiO is used
xx=0.95) as anode active material, the slurry of modulation containing Si oxide alloy active material, by weight percentage, the solid constituent of slurry contains the Si oxide of 90% as alloy anode active material, the sodium carboxymethylcellulose (CMC) of 5% is as bonding agent, and the conductive carbon black (SP) of 5% is as electronic conductor.Be uniformly coated on process Copper Foil two sides after high-speed stirred is uniformly dispersed, forced air drying, through roll-in, the operation such as cutting, soldering polar ear obtains anode strip.
embodiment 2:as different from Example 1: the thickness of copper foil base material is 9um, base material is stamped array that diameter is the hole 11 of 5 μm equably, porose 11 the gross area account for 20% of the whole anode strip gross area.Then SiO will be coated with
2lithium metallic particles be filled in hole 11, SiO
2the thickness of coating layer is 200nm, obtains anode collector 1 of the present invention.Anode active material is the mixture of Si-C alloy and graphite.
Other are identical with embodiment 1, repeat no more herein.
embodiment 3:as different from Example 1: the thickness of copper foil base material is 15um, base material is stamped array that aperture is the hole 11 of 2 μm equably, porose 11 the gross area account for 30% of the whole anode strip gross area.Then Li will be coated with
3the lithium metallic particles of N is filled in hole 11, Li
3the thickness of N coating layer is 50nm.Obtain anode collector 1 of the present invention.Anode active material is Si-C alloy.
Other are identical with embodiment 1, repeat no more herein.
embodiment 4:as different from Example 1: the thickness of copper foil base material is 20um, base material is stamped array that aperture is the hole 11 of 0.5 μm equably, and the porose gross area accounts for 40% of whole anode strip area.Then be filled in hole 11 by the lithium metallic particles being coated with SiC, the thickness of SiC coating layer is 40nm.Obtain anode collector 1 of the present invention.Anode active material is Si
0.9sn
0.1o
2-C alloy.
Other are identical with embodiment 1, repeat no more herein.
embodiment 5:as different from Example 1: the thickness of copper foil base material is 30um, base material is stamped array that aperture is the hole 11 of 3 μm equably, porose 11 the gross area account for 50% of whole anode strip area.Then Si will be coated with
3n
4lithium metallic particles be filled in hole 11, Si
3n
4the thickness of coating layer is 220nm, obtains anode collector 1 of the present invention.Anode active material is Si
0.87al
0.13o
2.
Other are identical with embodiment 1, repeat no more herein.
embodiment 6:as different from Example 1: the thickness of copper foil base material is 40um, base material is stamped array that aperture is the hole 11 of 7 μm equably, porose 11 the gross area account for 60% of whole anode strip area.Then SnO will be coated with
2lithium metallic particles be filled in hole 11, SnO
2the thickness of coating layer is 80nm, obtains anode collector 1 of the present invention.Anode active material is Si
43.2al
20fe
12sn
0.2.
Other are identical with embodiment 1, repeat no more herein.
embodiment 7:as different from Example 1: the thickness of copper foil base material is 9um, base material is stamped array that aperture is the hole 11 of 9 μm equably, porose 11 the gross area account for 70% of whole anode strip area.Anode active material is Si
43.2al
20fe
12sn
0.2-C.
Other are identical with embodiment 1, repeat no more herein.
comparative example 1:as different from Example 1; Without punching on Copper Foil, do not include lithium metallic particles yet.
Other are identical with embodiment 1, repeat no more herein.
comparative example 2:as different from Example 1; Without punching on Copper Foil, do not include lithium metallic particles yet.After anode strip roll process, according to the method for bibliographical information, sprinkle one deck lithium powder equably on anode strip surface as far as possible, then lithium powder is pressed in diaphragm and goes, prevent from coming off, obtained anode strip.
Other are identical with embodiment 1, repeat no more herein.
embodiment 8:present invention also offers lithium ion battery in, the barrier film comprising cathode sheets, anode strip and be arranged between described cathode sheets and anode strip, and electrolyte, wherein, anode strip is the anode strip of embodiment 1.
The assembling of lithium ion battery: the anode strip prepared and cathode sheets and membrane coil are coiled into battery core, anode strip is wherein the anode strip of embodiment 1, again battery core is put into packaging bag, inject nonaqueous electrolytic solution, after encapsulation, lithium ion battery is changed into and burn-in test.
embodiment 9:as different from Example 8, anode strip is the anode strip of embodiment 2.All the other, with embodiment 8, repeat no more here.
embodiment 10:as different from Example 8, anode strip is the anode strip of embodiment 3.All the other, with embodiment 8, repeat no more here.
embodiment 11:as different from Example 8, anode strip is the anode strip of embodiment 4.All the other, with embodiment 8, repeat no more here.
embodiment 12:as different from Example 8, anode strip is the anode strip of embodiment 5.All the other, with embodiment 8, repeat no more here.
embodiment 13:as different from Example 8, anode strip is the anode strip of embodiment 6.All the other, with embodiment 8, repeat no more here.
embodiment 14:as different from Example 8, anode strip is the anode strip of embodiment 7.All the other, with embodiment 8, repeat no more here.
comparative example 3:as different from Example 7, anode strip is the anode strip of comparative example 1.All the other, with embodiment 8, repeat no more here.
comparative example 4: as different from Example 7, anode strip is the anode strip of comparative example 2.All the other, with embodiment 8, repeat no more here.
Carry out the coulombic efficiency first ratio of discharge capacity and initial charge capacity (namely first) test to the battery of embodiment 8 to 14 and comparative example 3 and 4, acquired results is shown in table 1.
Disassemble the battery of embodiment 8 to the 14 and comparative example 3 and 4 prepared, take out anode strip, test its original depth, be designated as d1, after completely being filled by battery, disassemble battery, take out anode strip, then test the thickness d 2 of the anode strip after completely filling, calculate the thickness swelling of anode strip.Thickness swelling=(d2-d1)/d1 × 100%, acquired results is shown in table 1.
Table 1: the coulombic efficiency first of the battery of embodiment 8 to 14 and comparative example 3 and 4 and thickness swelling.
| Group | Coulombic efficiency first | Thickness swelling |
| Embodiment 1 | 86% | 24% |
| Embodiment 2 | 90% | 16% |
| Embodiment 3 | 92% | 27% |
| Embodiment 4 | 93% | 20% |
| Embodiment 5 | 94% | 22% |
| Embodiment 6 | 96% | 14% |
| Embodiment 7 | 98% | 18% |
| Comparative example 1 | 64% | 115% |
| Comparative example 2 | 80% | 84% |
As can be seen from Table 1, the coulombic efficiency first of embodiments of the invention 8 to 14 and comparative example 3 and 4 obviously improves.This is because the present invention adds lithium metallic particles in the hole 11 of anode collector 1, because the electromotive force of anode alloy materials and lithium metallic particles is uneven, having electrolyte to deposit in case, lithium metallic particles will melt in electrolyte, and then be embedded in anode alloy.In the process embedding anode alloy, be attended by the interaction of electrolyte solvent and anode active material, now have the SEI film of part to be formed.The preformed SEI film of this process, by the SEI film film-forming amount of minimizing battery in initial charge process, namely can reduce the consumption of battery cathode activity lithium ion in initial charge process, namely can improve the initial coulomb efficiency of battery.
Certainly, anode strip is in the process embedding lithium ion, and its material own vol will expand, and then will cause the expansion of anode strip.In embodiment 8 to 14, due to melting of lithium metallic particles, hole 11 vacancy in copper foil base material out, for the expansion of anode strip provides additional space, than comparative example 3 and 4, show less anode expansion, thus ensure the consistency of battery in size and chemical property.And the anode strip to adopt due to lithium battery of the present invention is alloy anode, therefore has very high energy density, has a extensive future.As can be seen from embodiment 8 to 14 and comparative example 4 relatively, although spreading lithium powder and then although the method for lithium powder press-in anode strip can be played the effect of supplementary battery irreversible capacity on anode strip of reporting in document, the expansion of battery cannot be improved.
In view of those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned execution mode; therefore; the present invention is not limited to embodiment disclosed and described above, within the protection range that also should fall into claim of the present invention to modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. an anode sheet of lithium ion battery, comprise anode collector and the anode diaphragm being arranged at described anode collector, described anode diaphragm comprises anode active material, binding agent and conductive agent, it is characterized in that: described anode active material comprises Si-C alloy, Si
ao
bm
cand Si
ao
bm
cat least one in-C alloy, wherein 0<a≤100,0≤b<100,0≤c<100, and be zero when b, c are different; M is at least one in aluminium, tin, manganese, indium, yttrium, molybdenum, niobium, tantalum, iron, copper, titanium, chromium, nickel, cobalt, zirconium, lanthanum and actinium element, and described anode collector arranges porose, is filled with lithium metallic particles in described hole.
2. anode sheet of lithium ion battery according to claim 1, is characterized in that: the thickness of described anode collector is less than or equal to 40 μm.
3. anode sheet of lithium ion battery according to claim 1, is characterized in that: the gross area in described hole is less than or equal to 70% with the gross area ratio of described anode strip.
4. anode sheet of lithium ion battery according to claim 3, is characterized in that: the gross area in described hole and the gross area of described anode strip are than being 10-50%.
5. anode sheet of lithium ion battery according to claim 4, is characterized in that: the gross area in described hole is 30% with the gross area ratio of described anode strip.
6. anode sheet of lithium ion battery according to claim 1, is characterized in that: described hole is uniformly distributed on the surface of described anode collector.
7. anode sheet of lithium ion battery according to claim 1, is characterized in that: the diameter in described hole is 0.01-10 μm.
8. anode sheet of lithium ion battery according to claim 1, is characterized in that: the Surface coating of described lithium metallic particles has at least one in carbon, metal oxide, metal carbides and metal nitride.
9. anode sheet of lithium ion battery according to claim 8, is characterized in that: the thickness of the coating layer of described lithium surface of metal particles is 30-300nm.
10. a lithium ion battery, the barrier film comprising cathode sheets, anode strip and be arranged between described cathode sheets and anode strip, and electrolyte, is characterized in that: described anode strip is the anode sheet of lithium ion battery described in any one of claim 1 to 9.
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| CN103794800B (en) * | 2012-11-02 | 2016-12-21 | 华为技术有限公司 | Lithium battery collector, pole piece and lithium battery and preparation method thereof, lithium battery applications |
| KR101621412B1 (en) * | 2013-09-11 | 2016-05-16 | 주식회사 엘지화학 | Lithium electrode and lithium secondary battery including the same |
| CN103490041B (en) * | 2013-10-08 | 2016-02-10 | 东莞新能源科技有限公司 | Lithium ion battery and rich lithium anode sheet thereof |
| TWI528619B (en) * | 2014-07-16 | 2016-04-01 | 輝能科技股份有限公司 | Lithium metal electrode |
| CN104091921A (en) * | 2014-07-22 | 2014-10-08 | 厦门首能科技有限公司 | Porous silicon and carbon mixed anode plate and lithium ion secondary battery comprising same |
| CN107369813B (en) * | 2016-05-12 | 2019-10-01 | 华为技术有限公司 | Metal lithium electrode and preparation method thereof, lithium metal second electrode cathode, battery |
| CN107706350B (en) * | 2017-10-16 | 2021-01-05 | 四川华昆能源有限责任公司 | Electrode structure of three-dimensional lithium anode and corresponding preparation method of lithium-sulfur battery |
| CN110635116B (en) | 2018-06-22 | 2021-10-22 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery |
| CN109786686A (en) * | 2018-12-17 | 2019-05-21 | 中南大学 | A kind of lithium cell cathode material and preparation method thereof, cathode of lithium battery and lithium battery |
| FR3091626B1 (en) * | 2019-01-08 | 2021-01-29 | Commissariat Energie Atomique | NEGATIVE ELECTRODES FOR USE IN ACCUMULATORS OPERATING ACCORDING TO THE PRINCIPLE OF IONIC INSERTION AND DISINSERTION OR OF ALLOY AND ACCUMULATOR FORMATION CONTAINING SUCH AN ELECTRODE |
| CN111430723A (en) * | 2020-04-26 | 2020-07-17 | 天津市捷威动力工业有限公司 | Lithium-supplementing current collector, preparation method and application thereof, negative pole piece and lithium ion battery |
| CN111540907A (en) * | 2020-05-11 | 2020-08-14 | 深圳新恒业电池科技有限公司 | Current collector, pole piece, lithium battery and preparation method of pole piece |
| EP4016707A1 (en) | 2020-12-15 | 2022-06-22 | Renata AG | A holder for an electrode of a button battery and a battery provided therewith |
| CN113594410B (en) * | 2021-07-29 | 2023-03-24 | 溧阳紫宸新材料科技有限公司 | Cathode structure, preparation method thereof and solid-state battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465416A (en) * | 2008-12-31 | 2009-06-24 | 大连海事大学 | High specific capacity composite electrode pole piece for lithium ion battery |
| CN101814372A (en) * | 2009-02-25 | 2010-08-25 | 富士重工业株式会社 | Electric storage device, and production method thereof |
| CN102437313A (en) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | Negative electrode for high-power metal lithium battery |
Family Cites Families (1)
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| US8974959B2 (en) * | 2008-07-16 | 2015-03-10 | Uchicago Argonne, Llc | Multi-component intermetallic electrodes for lithium batteries |
-
2012
- 2012-06-12 CN CN201210191929.8A patent/CN102683639B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465416A (en) * | 2008-12-31 | 2009-06-24 | 大连海事大学 | High specific capacity composite electrode pole piece for lithium ion battery |
| CN101814372A (en) * | 2009-02-25 | 2010-08-25 | 富士重工业株式会社 | Electric storage device, and production method thereof |
| CN102437313A (en) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | Negative electrode for high-power metal lithium battery |
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