CN102054968A - Surface activated cathode piece - Google Patents
Surface activated cathode piece Download PDFInfo
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- CN102054968A CN102054968A CN2010102363904A CN201010236390A CN102054968A CN 102054968 A CN102054968 A CN 102054968A CN 2010102363904 A CN2010102363904 A CN 2010102363904A CN 201010236390 A CN201010236390 A CN 201010236390A CN 102054968 A CN102054968 A CN 102054968A
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- film layer
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 16
- 230000003746 surface roughness Effects 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 8
- 239000010408 film Substances 0.000 description 39
- 229910002804 graphite Inorganic materials 0.000 description 38
- 239000010439 graphite Substances 0.000 description 38
- 238000004544 sputter deposition Methods 0.000 description 25
- 239000010949 copper Substances 0.000 description 23
- 238000000151 deposition Methods 0.000 description 20
- 230000008021 deposition Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000001755 magnetron sputter deposition Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910020328 SiSn Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 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
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000002391 graphite-based active material Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a surface activated cathode piece. The cathode piece is characterized in that a doped Si activation layer is arranged on a metal substrate, and a carbon film layer is arranged on the doped Si activation layer; doped elements in the doped Si activation layer are selected from a metallic element of Sn and Al and a nonmetallic element of C and O; the carbon film layer is an undefined structure; crystalline grains in the doped Si activation layer and the carbon film layer are of a nano scale; the thickness of the doped Si activation layer is 1-2,000nm; the thickness of the carbon film layer is 1-500nm; the doped Si activation layer and the carbon film layer can be sequentially arranged by multiple layers according to a sequence of doped Si activation layer/carbon film/doped Si activation layer/carbon film layer; a Cu foil is used as the metal substrate; and the surface roughness of the metal substrate is 0.1-10mum. In the surface activated cathode piece, the carbon film layer is utilized to protect the Si film layer, the doped elements are used as a buffer body, the surface roughness of the metal substrate is used for accommodating volume expansion, and the nano scale crystalline grains are used for accommodating volume changes of granules, so that the charge and discharge capacities of the cathode piece are large, and the cycle performance is greatly improved.
Description
Technical field
The present invention relates to lithium ion battery, particularly a kind of lithium ion battery surface active cathode pole piece.
Background technology
Along with dwindling of portable set size and volume, the more requirement of high-energy-density and power density is proposed lithium ion battery; The appearance of motor vehicle requires then that lithium ion battery has bigger discharge capability, size is littler, weight is lighter, cycle performance is more excellent.
For improving battery performance, important all the more for positive electrode, negative material and the electrolytical research of battery.
At present, the negative material of commercialization lithium ion battery mainly is to use various types of carbon-based materials, for example hard carbon, Delanium and native graphite etc., and wherein graphitic carbon, carbonaceous mesophase spherules is most widely used.The invertibity of graphite is outstanding, has guaranteed that battery has cycle life preferably.The theoretical specific capacity of graphite generally is no more than 372mAh/g, and the graphite active material density is low, and solid density is 2.2g/cc, and is therefore lower in the energy density of this class electrode.
The preparation process of traditional negative pole is relatively complicated, simply can be described as: at first prepare graphitic carbon or carbonaceous mesophase spherules powder, then add conductive agent, binding agent and other additive therein and form slurry, be coated with on the Cu matrix with coating machine then, finally make the lithium ion battery negative pole piece.
Silicon is a kind of novel negative material, and its theoretical specific capacity (4200mAh/g) is higher than the theoretical value (372mAh/g) of graphite far away.Silicon to discharge and recharge current potential similar to graphite, discharge voltage is smooth, the platform of charging and discharging curve is lower than 0.5V (V vsLi
+/ Li), but the application of the commerce of silicium cathode material but has been subjected to certain obstruction.Two wherein main problems are: 1, Si and Li in charge and discharge process
+Generation alloy/remove alloy reaction can produce bigger change in volume; 2, the solid amorphousization that drives of the electrochemistry that in alloying process first, is produced.Cycle performance is very poor when causing the Si material to use as the cathode pole piece of lithium ion battery thus.
DLC film or amorphous carbon film are covered the Si material surface, can suppress anodal growth and anodal degraded of going up skeleton, thereby prolong the life-span of the lithium ion battery that comprises negative pole.There is research to adopt adding that Li is not had active element as buffer body, perhaps between active material and metal substrate, apply a transition zone, be expected to improve the cycle performance of Si material, in addition, modification micron or nanostructure that employing can receiving volume be expanded, utilize diverse ways to prepare compound, be contained in the Li embedding thus and take off in the embedding process larger volume variation that particle takes place.But, these results of study, the cycle performance of the Si material that does not make significantly improves, and through tens charge and discharge cycles, it is still relatively more serious that the capacity sorrow subtracts situation.
Summary of the invention
For remedying above-mentioned deficiency, make full use of the excellent properties of Si material, the invention provides a kind of surface active cathode pole piece.
Surface active cathode pole piece of the present invention comprises metal substrate, wherein: be provided with doping Si active layer on metal substrate, a carbon film layer is set on doping Si active layer again;
Doped chemical is selected from a kind of metallic element among Sn, the Al and a kind of nonmetalloid among C, the O in the described doping Si active layer.
Described carbon film layer is a undefined structure.
Crystal grain in described doping Si active layer and the carbon film layer is nanoscale.
The thickness of described doping Si active layer is 1-2000nm.
The thickness of described carbon film layer is 1-500nm.
Described doping Si active layer and carbon film layer can be provided with by the order multilayer of doping Si active layer/carbon film layer/doping Si active layer/carbon film layer.
Described metal substrate is selected the Cu paper tinsel for use.
The surface roughness of described metal substrate is 0.1-10 μ m.
Surface active cathode pole piece of the present invention utilizes the carbon film layer, protection Si rete; Utilize doped chemical to make buffer body, utilize the surface roughness receiving volume of metal substrate to expand again, utilize nanometer-size die, hold the granule change in volume, make that this cathode pole piece charge/discharge capacity is big, cycle performance obtains bigger raising.
Description of drawings
Fig. 1 is the structure chart of surface active cathode pole piece of the present invention;
Fig. 2 is the sandwich construction figure of surface active cathode pole piece of the present invention;
Fig. 3 is the electrochemical properties resolution chart of surface active cathode pole piece of the present invention;
Fig. 4 is electron microscope scanning (SEM) photo of surface active cathode pole piece of the present invention;
Fig. 5 is the SEM photo after surface active cathode pole piece of the present invention carries out the electrochemical properties test;
Fig. 6 is the SEM photo of the film that deposits on the smooth metal substrate surface;
Fig. 7 is to be the SEM photo of the film that deposits on the Cu substrate surface of 5 μ m in surface roughness;
Fig. 8 is the cycle performance curve comparison diagram of embodiment 1-1 and comparative example 1 correspondence;
Fig. 9 is the cycle performance curve comparison diagram of embodiment 1-2 and comparative example 1 correspondence;
Figure 10 is the cycle performance curve comparison diagram of embodiment 1-3 and comparative example 1 correspondence;
Figure 11 is the cyclic curve comparison diagram of embodiment 2 and comparative example 2 correspondences;
Figure 12 is the cyclic curve comparison diagram of embodiment 3 and comparative example 3 correspondences;
Figure 13 is the cyclic curve comparison diagram of embodiment 4-1 and comparative example 4 correspondences;
Figure 14 is the cyclic curve comparison diagram of embodiment 4-2 and comparative example 4 correspondences;
Figure 15 is the cyclic curve comparison diagram of embodiment 4-3 and comparative example 4 correspondences.
Embodiment
Below in conjunction with embodiment surface active cathode pole piece of the present invention is done more detailed explanation.
The anode pole piece of using the lithium ion battery of surface active cathode pole piece of the present invention is prepared as follows: utilize solvent N-methyl pyrrolidone (NMP), disperse the mixture LiMO of composite oxides
Y(wherein M is at least a transition metal, as Co, Ni, Mn etc.) is as Li
XCoO
2, Li
XNiO
2, LiMn
2O
4, Li
XMnO
3Deng, use electric conducting material (as carbon black) and binding agent (as polyvinylidene fluoride) simultaneously, mix the formation slurry coating and on metal substrate (as aluminium foil), make.
The lithium ion battery of using surface active cathode pole piece of the present invention prepares according to following method: in dry environment or inert gas environment, lamination cathode pole piece and just positive sheet, the placing porous film is as barrier film (perforated membrane can by polyolefin such as polyethylene or polypropylene preparation) between anode pole piece and cathode pole piece.The battery that lamination is good is placed in the battery case, charges into liquid electrolyte or solid electrolyte and (all comprises lithium salts and solvent (as propylene carbonate, ethylene carbonate, butylene carbonate).
Surface active cathode pole piece of the present invention adopts the magnetron sputtering technique preparation, is target with doping Si target, graphite target respectively, and the Cu substrate is the base flow body, at Ar or Ar and CH
4, C
2H
2The mist work atmosphere in dopant deposition Si active layer plural layers alternate on the Cu paper tinsel successively with the carbon film layer, can deposit 2 layers, 4 layers (seeing Fig. 1, Fig. 2).Film thickness is as follows: the thickness of doping Si active layer must not surpass 2000nm, and the thickness of carbon film layer must not surpass 500nm.Doped chemical can be Al, Sn.
With Li as reference electrode, the chemical property (see figure 3) of under room temperature (25 ℃) condition, having tested the thin-film material of the different numbers of plies, the density that discharges and recharges that is adopted is 1mA/cm
2
Fig. 4, Figure 5 shows that the surface topography of the negative material of deposition, negative material and Cu paper tinsel substrate are in conjunction with tight, the configuration of surface of massif shape, the space has been reserved in the volumetric expansion and the contraction of producing for active material in the process of taking off embedding Li ion, changes the cycle performance that done good simultaneously.Surface topography behind the electro-chemical test is seen Fig. 5, and particle contacts still good with substrate, has a small amount of crack to exist, and is due to the stress that produces in the charge and discharge process.
Fig. 6, Fig. 7 are seen in the contrast of using smooth copper foil and coarse Copper Foil to make substrate, its form has bigger difference, when selecting coarse Copper Foil to make substrate, can increase the adhesion of film and substrate, for the change in volume that embeds, takes place when taking off embedding Li ion provides the cushion space (see figure 7), improve the chemical property of Si active layer to a certain extent in charge and discharge process.
Embodiment 1-1:
Utilize radiofrequency magnetron sputtering technology, with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
XAl
YC
Z/ C/Si
XAl
YC
Z/ C composite membrane, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 200W, and gas Ar flow is 58sccm.During the deposit carbon rete, graphite sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.In doping Si active layer, the atomic ratio of Si: Al: C is about 100: 50: 20.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 1-2:
Utilize radiofrequency magnetron sputtering technology, with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
XAl
YC
Z/ C/Si
XAl
YC
Z/ C composite membrane, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 150W, and gas Ar flow is 58sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.In doping Si active layer, the atomic ratio of Si: Al: C is about 100: 50: 5.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 1-3:
Utilize radiofrequency magnetron sputtering technology, with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
XAl
YC
Z/ C/Si
XAl
YC
Z/ C composite membrane, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 58sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.In doping Si active layer, the atomic ratio of Si: Al: C is about 100: 1: 1.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Comparative example 1:
Utilizing radiofrequency magnetron sputtering technology, is target with crystal Si target, graphite target, is deposition Si/C/Si/C composite membrane on the Cu paper tinsel of 15 μ m at thickness, during deposition Si layer, Si target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 58sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 1-1,1-2,1-3 and comparative example 1 pairing thin film electrochemistry cycle performance curve are seen Fig. 8, Fig. 9, Figure 10, this shows that through element doping, make the chemical property of Si base film be improved, cycle performance is improved.
Embodiment 2:
Utilizing the magnetically controlled DC sputtering technology, is target with crystal SiAl assembly target, graphite target, gas Ar, O
2Being the doping working gas, is to deposit Si on the Cu paper tinsel of 15 μ m at thickness
XAl
YC
Z/ C/Si
XAl
YC
Z/ C composite membrane, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 58sccm, O
2Flow is 15sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.In doping Si active layer, the atomic ratio of Si: Al: O is about 100: 50: 5.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Comparative example 2:
Utilizing radiofrequency magnetron sputtering technology, is target with crystal Si target, graphite target, is deposition Si/C/Si/C composite membrane on the Cu paper tinsel of 15 μ m at thickness, during deposition Si layer, Si target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 58sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 36sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 2 and comparative example 2 pairing thin film electrochemistries follow bad performance curve and see Figure 11, as seen mix through oxygen element, make the chemical property of Si film be improved, and cycle performance is improved.
Embodiment 3:
Utilize radiofrequency magnetron sputtering technology, with crystal SiSn piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
XSn
Y/ C/Si
XSn
Y/ C composite membrane, deposition Si
XSn
YDuring active layer, SiSn target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 78sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 66sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Comparative example 2:
Utilizing radiofrequency magnetron sputtering technology, is target with crystal Si target, graphite target, is deposition Si/C/Si/C composite membrane on the Cu paper tinsel of 15 μ m at thickness, during deposition Si layer, Si target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 78sccm.During the deposit carbon rete, graphite target sputtering power 400W, Ar flow are 66sccm.Each layer thickness of gained laminated film is respectively 500nm/50nm/500nm/50nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 3 and comparative example 3 pairing thin film electrochemistries follow bad performance curve and see Figure 11, as seen pass through the Sn element doping, make the chemical property of Si film be improved, and cycle performance is improved.
Embodiment 4-1:
Direct current control sputtering technology is penetrated in utilization, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (roughness of Cu paper tinsel the is 0.1 μ m) Si of 12 μ m at thickness
XAl
YC
ZLaminated film, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm.During the deposit carbon rete, gained laminated film thickness is 2000nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 4-2:
Direct current control sputtering technology is penetrated in utilization, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (roughness of Cu paper tinsel the is 5 μ m) Si of 12 μ m at thickness
XAl
YC
ZLaminated film, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm.During the deposit carbon rete, gained laminated film thickness is 2000nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 4-3:
Direct current control sputtering technology is penetrated in utilization, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (roughness of Cu paper tinsel the is 10 μ m) Si of 12 μ m at thickness
XAl
YC
ZLaminated film, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm.During the deposit carbon rete, gained laminated film thickness is 2000nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Comparative example 4:
Direct current control sputtering technology is penetrated in utilization, with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the smooth Cu paper tinsel of 12 μ m
XAl
YC
ZLaminated film, deposition Si
XAl
YC
ZDuring active layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm.During the deposit carbon rete, gained laminated film thickness is 2000nm.Gained cathode pole piece and lithium metal composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio is 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is 0-2.0V.
Embodiment 4-1,4-2,4-3 and comparative example 4 pairing thin film electrochemistry cycle performance curves are seen Figure 13, Figure 14, Figure 15, this shows to have the film that deposits on the Cu paper tinsel of rough surface, and cycle performance obviously is better than the film that deposits on the smooth Cu paper tinsel.
Claims (8)
1. a surface active cathode pole piece comprises metal substrate, it is characterized in that: be provided with doping Si active layer on metal substrate, a carbon film layer is set on doping Si active layer again;
Doped chemical is selected from a kind of metallic element among Sn, the Al and a kind of nonmetalloid among C, the O in the described doping Si active layer.
2. surface active cathode pole piece according to claim 1 is characterized in that: described carbon film layer is a undefined structure.
3. surface active cathode pole piece according to claim 2 is characterized in that: the crystal grain in described doping Si active layer and the carbon film layer is nanoscale.
4. surface active cathode pole piece according to claim 3 is characterized in that: the thickness of described doping S active layer is 1-2000nm.
5. surface active cathode pole piece according to claim 4 is characterized in that: the thickness of described carbon film layer is 1-500nm.
6. surface active cathode pole piece according to claim 5 is characterized in that: described doping Si active layer and carbon film layer can be provided with by the order multilayer of doping Si active layer/carbon film layer/doping Si active layer/carbon film layer.
7. surface active cathode pole piece according to claim 6 is characterized in that: described metal substrate is selected the Cu paper tinsel for use.
8. surface active cathode pole piece according to claim 7 is characterized in that: the surface roughness of described metal substrate is 0.1-10 μ m.
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| CN2010102363904A CN102054968A (en) | 2010-07-22 | 2010-07-22 | Surface activated cathode piece |
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| CN2010102363904A CN102054968A (en) | 2010-07-22 | 2010-07-22 | Surface activated cathode piece |
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| CN102054968A true CN102054968A (en) | 2011-05-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN104347842A (en) * | 2013-07-23 | 2015-02-11 | 华为技术有限公司 | Composite negative electrode sheet of lithium ion secondary battery, preparation method thereof, and lithium ion secondary battery |
| CN105762323A (en) * | 2016-01-07 | 2016-07-13 | 惠州市佰特瑞科技有限公司 | Nanocarbon cathode of all-solid-state thin-film lithium ion battery and pareparation method of nanocarbon cathode |
| CN108134045A (en) * | 2017-12-12 | 2018-06-08 | 江苏双登富朗特新能源有限公司 | The silicon-carbon electrode of the external coating of lithium ion battery and coating paste formula |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271974A (en) * | 2007-03-22 | 2008-09-24 | 中信国安盟固利新能源科技有限公司 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271974A (en) * | 2007-03-22 | 2008-09-24 | 中信国安盟固利新能源科技有限公司 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN104347842A (en) * | 2013-07-23 | 2015-02-11 | 华为技术有限公司 | Composite negative electrode sheet of lithium ion secondary battery, preparation method thereof, and lithium ion secondary battery |
| CN104347842B (en) * | 2013-07-23 | 2017-08-25 | 华为技术有限公司 | A kind of lithium rechargeable battery composite negative plate and preparation method thereof and lithium rechargeable battery |
| CN105762323A (en) * | 2016-01-07 | 2016-07-13 | 惠州市佰特瑞科技有限公司 | Nanocarbon cathode of all-solid-state thin-film lithium ion battery and pareparation method of nanocarbon cathode |
| CN105762323B (en) * | 2016-01-07 | 2018-08-24 | 惠州市佰特瑞科技有限公司 | Solid-State Thin Film Li-Ion Batteries nanometer Carbon anode and preparation method thereof |
| CN108134045A (en) * | 2017-12-12 | 2018-06-08 | 江苏双登富朗特新能源有限公司 | The silicon-carbon electrode of the external coating of lithium ion battery and coating paste formula |
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Application publication date: 20110511 |