CN103066265A - Sodium ion battery negative pole active substance and preparation method and application thereof - Google Patents
Sodium ion battery negative pole active substance and preparation method and application thereof Download PDFInfo
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- CN103066265A CN103066265A CN2011103263772A CN201110326377A CN103066265A CN 103066265 A CN103066265 A CN 103066265A CN 2011103263772 A CN2011103263772 A CN 2011103263772A CN 201110326377 A CN201110326377 A CN 201110326377A CN 103066265 A CN103066265 A CN 103066265A
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- negative electrode
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- ion battery
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000013543 active substance Substances 0.000 title 1
- 239000007773 negative electrode material Substances 0.000 claims abstract description 92
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000002608 ionic liquid Chemical class 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical class OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical class OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002482 conductive additive Substances 0.000 claims description 4
- 239000008103 glucose Chemical class 0.000 claims description 4
- 229920000620 organic polymer Chemical class 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- AREPHAPHABGCQP-UHFFFAOYSA-N 1-(dimethylamino)-3-[2-[2-(4-methoxyphenyl)ethyl]phenoxy]propan-2-ol Chemical compound C1=CC(OC)=CC=C1CCC1=CC=CC=C1OCC(O)CN(C)C AREPHAPHABGCQP-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000840 electrochemical analysis Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000009837 dry grinding Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 101100001675 Emericella variicolor andJ gene Proteins 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 241000590419 Polygonia interrogationis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MKHFCTXNDRMIDR-UHFFFAOYSA-N cyanoiminomethylideneazanide;1-ethyl-3-methylimidazol-3-ium Chemical compound [N-]=C=NC#N.CCN1C=C[N+](C)=C1 MKHFCTXNDRMIDR-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明提供了一种钠离子电池负极活性物质，其中，所述负极活性物质的通式为Li4-xM1 xTi5-yM2 yO12，其中，M1选自Na、Mg、Al、Si、K、Ca、V、Cr、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Ag、In、Sn、La、Ce、Ta、W、La和Ce，M2选自Li、Na、Mg、Al、Si、K、Ca、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Ag、In、Sn、Ta、W、La或Ce，0≤x≤4，0≤y≤0.5；优选地，M1选自Na、Cu，M2选自Mg、Al、Cu、Zn、Zr、Nb，0≤x≤2，0≤y≤0.2；更优选地，M1选自Na，M2选自Mg、Al、Cu、Nb，0≤x≤1，0≤y≤0.05。本发明还提供了所述负极活性物质的制备方法，以及其用于制备钠离子电池负极材料、负极或钠离子电池的应用。
The present invention provides a negative electrode active material for a sodium ion battery, wherein the general formula of the negative electrode active material is Li 4-x M 1 x Ti 5-y M 2 y O 12 , wherein M 1 is selected from Na, Mg , Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta, W, La and Ce , M2 is selected from Li, Na, Mg, Al, Si, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In , Sn, Ta, W, La or Ce, 0≤x≤4, 0≤y≤0.5; preferably, M1 is selected from Na, Cu, M2 is selected from Mg, Al, Cu, Zn, Zr, Nb, 0≤x≤2, 0≤y≤0.2; more preferably, M1 is selected from Na, M2 is selected from Mg, Al, Cu, Nb, 0≤x≤1, 0≤y≤0.05. The present invention also provides a preparation method of the negative electrode active material, and its application for preparing a negative electrode material for a sodium ion battery, a negative electrode or a sodium ion battery.
Description
Technical field
The present invention relates to a kind of sodium-ion battery negative electrode active material and its preparation method and application, be specifically related to the higher sodium-ion battery negative electrode active material of a kind of current potential platform, its preparation method reaches the application for the preparation of anode material of lithium-ion battery, negative pole and sodium-ion battery.
Background technology
Since the end of the eighties, Sony company produced first lithium ion battery, with its high-energy-density, long circulation life, the characteristics such as environmental pollution is little, on miniaturized electronics, be widely used, and begin in recent years to be applied to electric motor car and large-scale energy storage device.
But along with the day by day consumption of lithium resource, people begin to turn one's attention to the more sodium of horn of plenty of resource.About the at present existing many reports of the positive active material that is used for sodium-ion battery, such as the Na of NASICON structure
3Fe
2(PO
4)
3(C.Delmas, F.Cherkaoui, et.al., Mater.Res.Bull.22,631 (1987)), NaTi
2(PO
4)
3(S.Okada, T.Yamamoto, et.al., J.Power Sources, 146,570-574 (2005)), metal sulfide FeS
2, TiS
2And oxide Na
0.44MnO
2(Sauvage F.; Laffont L.; Tarascon J.-M.et.al., Inorganic Chemistry, 46,3289 (1996)).But the negative material of sodium-ion battery rarely has report in addition except hard carbon ball (D.A.Steven andJ.R.Dahn, J.Electrochem.Soc., 147,1271 (2000)).With question marks in lithium ion battery seemingly because the current potential platform of hard carbon material is lower, be easy to form in negative terminal surface the deposition of sodium metal, cause sode cell to have potential safety hazard.
Because there are larger difference in lithium ion battery and sodium-ion battery in all many-sides, greater than lithium ion, many oxidation-reduction pairs are with respect to Na such as the sodium ion radius
+The current potential of/Na is usually than Li
+Therefore the low 0.3～0.5V of/Li etc. directly apply to sodium-ion battery with the negative electrode active material of lithium ion battery and are difficult to satisfy instructions for use.For example, the graphite cathode that generally uses in the commercial batteries at present, the capacity of its embedding sodium is very low and can not circulate; And for example, the high power capacity negative material silicon in the lithium ion battery does not have the activity of embedding sodium yet.At present, still need continue to seek and have high taking off/negative material of embedding sodium current potential.
Summary of the invention
Therefore, the object of the invention is to overcome present anode material of lithium-ion battery current potential lower and easily form the defective of sodian deposition, a kind of sodium-ion battery negative electrode active material with high potential platform and its preparation method and application is provided.
The invention provides a kind of sodium-ion battery negative electrode active material, the general formula of this negative electrode active material is Li
4-xM
1 xTi
5-yM
2 yO
12, wherein, M
1Be doped metal ion, can be selected from Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta, W, La or Ce, M
2Be doped metal ion, can be selected from Li, Na, Mg, Al, Si, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La or Ce, 0≤x≤4,0≤y≤0.5.For example, work as M
2Be Mg, x=0, during y=0.05, the chemical formula of described negative electrode active material is Li
4Ti
4.95Mg
0.05O
12
As preferably, M
1Can be selected from Na, Cu, M
2Can be selected from Mg, Al, Cu, Zn, Zr, Nb, 0≤x≤2,0≤y≤0.2.As more preferably, M
1Can be selected from Na, M
2Can be selected from Mg, Al, Cu, Nb, 0≤x≤1,0≤y≤0.05.
According to negative electrode active material of the present invention, wherein, described negative electrode active material can be coated with one or more of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer.
According to negative electrode active material of the present invention, wherein, the thickness of described carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer can be 1～10nm independently of one another.
The present invention also provides the preparation method of described negative electrode active material, and described preparation method can be selected from any in spray drying process, solid phase method or the sol-gel process.
Described spray drying process can for: with carbonate, titanyl compound, the M of lithium
1Compound, M
2Compound mix according to the stoichiometric proportion of negative electrode active material, also grind evenly take ethanol as solvent, spray-dried precursor powder places in the crucible gained precursor powder in 650～1000 ℃ of lower processing 2～20 hours, grinds and namely gets described negative electrode active material.
Described solid phase method can for: with hydroxide, titanyl compound, the M of lithium
1Compound, M
2Compound mix according to the stoichiometric proportion of negative electrode active material, after grinding evenly precursor powder, the gained precursor powder is placed in the crucible in 650～1000 ℃ of lower processing 2～20 hours, grind and namely get described negative electrode active material.
Described sol-gel process is: the stoichiometric proportion according to negative electrode active material takes by weighing an amount of lithium acetate and butyl titanate and is dissolved in respectively absolute ethyl alcohol, ethanol solution with lithium acetate in whipping process slowly joins in the ethanol solution of butyl titanate, and adding citric acid, form aqueous precursor gel, place crucible in 650～1000 ℃ of lower processing 2～20 hours the gained aqueous precursor gel, grind and namely get described negative electrode active material.
Preparation in accordance with the present invention, wherein, can adopt in the following methods any that described negative electrode active material is coated one or more of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer: (1) adds sucrose, glucose, organic polymer, ionic liquid or slaine in described precursor powder or gel; (2) in described negative electrode active material, add sucrose, glucose, organic polymer, ionic liquid or slaine, and under Buchholz protection heat treated; (3) adopt the thermal vapor deposition method that described presoma or described negative electrode active material are coated.
The invention provides a kind of anode material of lithium-ion battery, described negative material can comprise conductive additive and binding agent, the negative electrode active material that can also comprise negative electrode active material of the present invention or make according to preparation method of the present invention.
The invention provides a kind of sodium-ion battery negative pole, described negative pole can comprise negative material of the present invention and collector.
The invention provides a kind of sodium-ion battery, described sodium-ion battery can comprise anodal and negative pole of the present invention, and places barrier film and electrolyte between described positive pole and the described negative pole.
Described negative electrode active material during for the preparation of anode material of lithium-ion battery and negative pole, can be adopted the general manufacture method of existing lithium ion battery.That is, with negative electrode active material of the present invention with as the powder of conductive additive (such as carbon black, acetylene black, graphite powder, carbon nano-tube, graphite rare etc.) ground and mixed, described conductive additive accounts for 0～20wt%.Then with general binder solution, for example can be NMP (1-METHYLPYRROLIDONE) solution of PVDF (polyvinylidene fluoride), be mixed into uniform sizing material, be coated on (such as Copper Foil, titanium foil, nickel screen, nickel foam etc.) preparation electrode slice on the collector, the thickness of gained film can be 2～500 μ m after applying.The electrode obtained sheet is cut into suitable shape, and 100～150 ℃ of lower oven dry are rear for subsequent use in being essentially the environment of vacuum.
The improvements of described sodium-ion battery are to use negative electrode active material provided by the invention, and other part and preparation method are conventionally known to one of skill in the art, repeat no more herein.Described sodium-ion battery can be water system, non-water or all solid state sodium-ion battery.Described sodium-ion battery have cost low, have extended cycle life, the energy density high, can be widely used in solar energy, the required extensive energy storage device of wind power generation, and the field such as intelligent grid peak regulation, distribution power station, back-up source, communication base station, especially be suitable as extensive energy storage device.
The present invention also provides the application of described negative electrode active material for the preparation of anode material of lithium-ion battery, negative pole and sodium-ion battery.
Sodium-ion battery negative electrode active material of the present invention has higher current potential platform (can reach 0.8～0.9V), the phenomenon that can effectively avoid sodium metal to deposit at negative pole, (first all discharge capacities are greater than 180mAh/g under C/10 also to have good capacity density and coulombic efficiency, coulombic efficiency can reach approximately 84%), thereby the invention provides and a kind ofly have high potential platform, safe and capacity density and the well behaved sodium-ion battery negative electrode active material of enclosed pasture efficient, and the negative material and the sodium-ion battery that comprise this negative electrode active material.
Description of drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 shows ESEM (SEM) figure of the negative electrode active material of the embodiment of the invention 1;
Fig. 2 shows X-ray diffraction (XRD) collection of illustrative plates of the negative electrode active material of the embodiment of the invention 1;
Fig. 3 shows the last fortnight charging and discharging curve of the sodium-ion battery of the embodiment of the invention 1;
Fig. 4 shows the last fortnight charging and discharging curve of the sodium-ion battery of the embodiment of the invention 2;
Fig. 5 shows the first five all charging and discharging curve of the sodium-ion battery of the embodiment of the invention 3;
Fig. 6 shows the first and the 5th all charging and discharging curves of the sodium-ion battery of the embodiment of the invention 6;
Fig. 7 shows the last fortnight charging and discharging curve of the sodium-ion battery of Comparative Examples 1.
Embodiment
Further specify the present invention below by specific embodiment, still, should be understood to, these embodiment are only used for the usefulness that specifically describes more in detail, and should not be construed as for limiting in any form the present invention.
General description is carried out to the material and the test method that use in the present invention's test in this part.Although for realizing that the employed many materials of the object of the invention and method of operation are well known in the art, the present invention still does to describe in detail as far as possible at this.It will be apparent to those skilled in the art that in context, if do not specify, material therefor of the present invention and method of operation are well known in the art.
Embodiment 1
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts spray drying process to prepare negative electrode active material Li
4Ti
5O
12, concrete steps are: with nano-anatase TiO
2(grain diameter is 50～100nm) and Li
2CO
3(analyzing pure) mixes by stoichiometric proportion, and take alcohol as solvent, 900 rev/mins were mixed 4 hours in agate jar, obtained milky precursor pulp; The gained precursor pulp is carried out spray drying, and drying parameter is set to: inner drying pipe temperature is 100 ℃, and outer drying tube temperature is 70 ℃, and flow rate of slurry is approximately 500 ml/hours, obtains the precursor powder of white in the rewinding bottle; Precursor powder is transferred to Al
2O
3In the crucible, 800 ℃ of lower processing 10 hours in Muffle furnace, the gained white powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
4Ti
5O
12, its SEM figure and XRD collection of illustrative plates are seen Fig. 1 and Fig. 2.Can be found out by Fig. 1 and Fig. 2, this negative electrode active material is that particle diameter is the spherical honeycombed grain of 2～8 μ m, and is Li
4Ti
5O
12Pure phase.
Above-mentioned negative electrode active material is prepared into sodium-ion battery.Concrete steps are: with the negative electrode active material Li for preparing
4Ti
5O
12Powder mixes according to 80: 10: 10 weight ratio with acetylene black, binding agent PVDF, add an amount of nmp solution, in the environment of air drying, grind and form slurry, then slurry evenly is coated on copper foil of affluxion body or the aluminium foil, be cut into the pole piece of 8 * 8mm after the drying, under vacuum condition, in 100 ℃ of dryings 10 hours, be transferred to immediately glove box for subsequent use.Carry out in the glove box that is assemblied in Ar atmosphere of simulated battery, with the sodium metal sheet as to electrode, the NaPF of 1M
6/ PC (propylene carbonate) solution take glass fibre as barrier film, is assembled into the CR2032 button cell as electrolyte.Use the constant current charge-discharge pattern to test, discharge is 0.5V by voltage, and charging is 3.0V by voltage, and all tests are all carried out under the C/10 current density.Test result is seen Fig. 3, and wherein a1, a2, b1, b2 are respectively first all charging curves, first all discharge curves, second week charging curve, second week discharge curve.Found out by Fig. 3, its first all discharge capacity can reach 185mAh/g, and first all coulombic efficiencies are about 83.3%, and charge and discharge current potential platform is about 0.8～1.0V.
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts solid phase method to prepare negative electrode active material Li
4Ti
4.95Mg
0.05O
12, concrete steps are: with TiO
2, Li (OH)
2And Mg (OH)
2Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of white; The gained precursor powder is transferred to Al
2O
3In the crucible, 800 ℃ of heat treatment is 10 hours in the air atmosphere, and the gained white powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
4Ti
4.95Mg
0.05O
12
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result is seen Fig. 4, and wherein c1, c2, d1, d2 are respectively first all charging curves, first all discharge curves, second week charging curve, second week discharge curve.As seen from Figure 4, its first all discharge capacity can reach 193mAh/g, and first all coulombic efficiencies are about 80.3%, and capacity is 130mAh/g after five weeks of circulation, and charge and discharge current potential platform is about 0.8～1.0V.
Embodiment 3
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts sol-gel process to prepare negative electrode active material Li
4Ti
5O
12, and it is carried out the carbon coating process.Concrete steps are: with butyl titanate (Ti (C
4H
9O)
4) and lithium acetate (CH
3COOLi) take by weighing in right amount according to stoichiometric proportion, and be dissolved in respectively absolute ethyl alcohol.Ethanol solution with lithium acetate in whipping process joins in the ethanol solution of carbonic acid four butyl esters gradually, and adds an amount of citric acid to suppress hydrolysis, forms gradually aqueous precursor gel, and the gained aqueous precursor gel is transferred to Al
2O
3In 800 ℃ of lower processing 20 hours, obtain white powder after the grinding for subsequent use in the crucible.This white powder and ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methy limidazolium dicyanamide) are mixed, and in Ar atmosphere, carry out pyrolysis in 600 ℃ of heating 4h, namely obtain the negative electrode active material Li that carbon coats after the cooling
4Ti
5O
12/ C, wherein the thickness of carbon-coating is essentially 1～10nm.Also can use other feasible methods that described negative electrode active material is coated carbon-coating, perhaps covered with metal layer, nitride layer, oxide skin(coating) and high polymer layer etc. herein.
The negative electrode active material that above-mentioned carbon is coated is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are carried out the discharge of 100mAh/g limited capacity with embodiment 1 to battery, and test result is seen Fig. 5, and wherein e1, e2 are respectively first all charging curves and first all discharge curves.As seen from Figure 5, its first all charging capacity can reach 184mAh/g, and first all coulombic efficiencies are about 84%, and charge and discharge current potential platform is about 0.8～1.0V.
Embodiment 4
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts solid phase method to prepare negative electrode active material Li
4Ti
4.97Al
0.03O
12, concrete steps are: with TiO
2, Li (OH)
2And Al (OH)
3Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of white; The gained precursor powder is transferred to Al
2O
3In the crucible, 650 ℃ of heat treatment is 20 hours in the air atmosphere, and the gained white powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
4Ti
4.97Al
0.03O
12
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Its first all discharge capacity can reach 190mAh/g, and first all coulombic efficiencies are about 82%, and capacity is 136mAh/g after five weeks of circulation, and charge and discharge current potential platform is about 0.8～1.0V.
Embodiment 5
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts solid phase method to prepare negative electrode active material Li
4Ti
4.85Cu
0.15O
12, concrete steps are: with TiO
2, Li (OH)
2And Cu (NO
3)
2Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of cyan; The gained precursor powder is transferred to Al
2O
3In the crucible, 800 ℃ of heat treatment is 2 hours in the air atmosphere, and the gained pale powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
4Ti
4.5Cu
0.5O
12
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Its first all discharge capacity can reach 184mAh/g, and first all coulombic efficiencies are about 82.1%, and capacity is 146mAh/g after five weeks of circulation, and charge and discharge current potential platform is about 0.72～1.0V.
Embodiment 6
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts solid phase method to prepare negative electrode active material Li
4Ti
4.98Nb
0.02O
12, concrete steps are: with TiO
2, Li (OH)
2And Nb
2O
5Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of white; The gained precursor powder is transferred to Al
2O
3In the crucible, 1000 ℃ of heat treatment is 10 hours under air atmosphere, and the gained powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
4Ti
4.98Nb
0.02O
12
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result is seen Fig. 6, and wherein f1, f2, g1, g2 are respectively first all charging curves, first all discharge curves, the 5th all charging curves, the 5th all discharge curves.As seen from Figure 6, its first all discharge capacity can reach 192mAh/g, and first all coulombic efficiencies are about 74%, and capacity is 141mAh/g after five weeks of circulation, and charge and discharge current potential platform is about 0.75～0.97V.
Embodiment 7
The present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The present embodiment adopts solid phase method to prepare negative electrode active material Li
3.9Na
0.1Ti
5O
12, concrete steps are: with TiO
2, Li
2CO
3, Na
2CO
3Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of white; The gained precursor powder is transferred to Al
2O
3In the crucible, 800 ℃ of heat treatment is 10 hours under air atmosphere, and the gained white powder is for subsequent use after grinding, and is negative electrode active material Li of the present invention
3.9Na
0.1Ti
5O
12
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Its first all discharge capacity is 180mAh/g, and first all coulombic efficiencies are about 82%, and the capacity after five weeks of circulating is 140mAh/g, and charge and discharge current potential platform is about 0.7～0.9V.
Comparative Examples 1
This Comparative Examples is used for the preparation of the sodium-ion battery of explanation take hard carbon material as negative pole.
Hard carbon material and binding agent PVDF are mixed with 95: 5 weight ratio, add an amount of nmp solution, in the environment of air drying, grind and form slurry, then evenly be coated on slurry on the Copper Foil, be cut into the pole piece of 8 * 8mm after the drying, under vacuum condition, in 100 ℃ of dryings 10 hours, be transferred to immediately glove box for subsequent use.Battery assembly method and electrochemical test method are with embodiment 1.
0.01～3V test result of this sodium-ion battery is seen Fig. 7, and wherein h1, h2, i1, i2 are respectively first all charging curves, first all discharge curves, second week charging curve, second week discharge curve.As seen from the figure, first all discharge capacities of the sodium-ion battery take hard carbon material as negative pole are 290mAh/g, first all efficient is 67%, its discharge platform than many parts below 0.1V, sedimentation potential close to sodium metal, be very easy to cause sodian deposition, will cause safely adverse effect to the use of full battery.Its coulombic efficiency is low simultaneously, has wasted positive electrode capacity.
And the charging/discharging voltage platform of sodium-ion battery that adopts negative electrode active material of the present invention is substantially at 0.7～0.9V, the safety issue that can avoid sodian deposition to bring; Its first all efficient can reach 84%, and reversible capacity generally can reach 150mAh/g, shows good electrochemical properties.Significantly, negative electrode active material provided by the present invention more meets the use needs as the negative pole of sodium-ion battery than traditional hard carbon material.
Although the present invention has carried out description to a certain degree, significantly, under the condition that does not break away from the spirit and scope of the present invention, can the suitable variation of each condition of carrying out.Be appreciated that to the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the replacement that is equal to of described each factor.
Claims (9)
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