CN100537418C - Preparation method of transition element doped iron lithium phosphate powder - Google Patents
Preparation method of transition element doped iron lithium phosphate powder Download PDFInfo
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- CN100537418C CN100537418C CNB2005101324282A CN200510132428A CN100537418C CN 100537418 C CN100537418 C CN 100537418C CN B2005101324282 A CNB2005101324282 A CN B2005101324282A CN 200510132428 A CN200510132428 A CN 200510132428A CN 100537418 C CN100537418 C CN 100537418C
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- 230000007704 transition Effects 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims abstract description 31
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 25
- 239000007774 positive electrode material Substances 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 26
- 238000007599 discharging Methods 0.000 description 25
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000005338 frosted glass Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- 230000004087 circulation Effects 0.000 description 12
- 238000009413 insulation Methods 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- -1 vitriol Chemical compound 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VOEZDMCKEMNFOS-UHFFFAOYSA-N manganese oxalic acid dihydrate Chemical compound O.O.[Mn].OC(=O)C(O)=O VOEZDMCKEMNFOS-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001002 morphogenetic effect Effects 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a preparation method of transition element Mn, Co and Ni doped iron lithium phosphate powder body, belonging to the field of electrochemical power supply material preparation technology. Its molecular formula is Li1-x TRxFePO4, and its preparation method includes the following steps: weighting lithium salt, ferrous salt, phosphate and adulterant according to mole ratio, mixing them, drying, low-temperature prebaking and high-temperature secondary calcining so as to obtain the invented product which can be used as positive electrode material of lithium ion cell.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material.Be particularly related to as using secondary lithium battery or power source preparation method always with a kind of transition element doped iron lithium phosphate powder of modification lithium-ion battery anode material.
Technical background
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, numerous advantages such as have that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile telephone, notebook computer, portable power tool, electronic instrument, weaponry etc., in electromobile, also have a good application prospect, become the emphasis that competitively research and develop countries in the world at present.Positive electrode material is an important component part of lithium ion battery, in the lithium ion battery charge and discharge process, not only to be provided in the positive and negative electrode lithium intercalation compound the needed lithium of back and forth embedding/take off, form the needed lithium of SEI film but also will bear the negative material surface, therefore, research and develop the key point that high performance positive electrode material has become the lithium ion battery development.Present research mainly concentrates on and contains lithium transition element metal oxide aspect, and the transition element metal is mainly cobalt, nickel, manganese.In recent years, based on Fe
3+/ Fe
2+The material of redox couple causes people's very big interest, particularly has the iron lithium phosphate (LiFePO of olivine crystal structure
4) become the most promising alternative positive electrode material of recent research.
LiFePO
4That material has is cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, multiple advantage such as capacity is higher, stability is fine.Goodenough[J.Electrochem.Soc., 144 (1997) 1188] research group has synthesized iron lithium phosphate (LiFePO at first
4), this material has high theoretical specific storage (170mAh/g) as anode material for lithium-ion batteries, greater than commercial LiCoO
2Actual discharge specific storage 140mAh/g, so cause investigator's very big concern.But the electronic conductivity of this material is relatively poor, has greatly limited the application of material under higher current density.The method about this material property of improvement raising of report mainly contains the surface and mixes or coated with conductive carbon material or conductive metal particle at present, improves the intergranular electronic conductivity of fertile material; Relatively large transition element replaces Fe
2+The position, the ionic conductivity of raising material; Partly replace Li and mix micro-high volence metal ion
+Electronic conductivity in the precursor granule can be improved in the position, is a kind of important method of modifying.Chung, S.Y., Chiang, Y.M. etc. (nature material version, NatuTR materials,, 1 volume, October, 123 pages in 2003) at first use a small amount of high volence metal ion Mg
2+, Al
3+, Ti
4+, Zr
2+, Nb
5+, W
6+Li doped FePO
4, the bigger LiFePO that improved
4Specific conductivity, make LiFePO
4Under high charge-discharge magnification, also have the capacity more than the 60mAh/g, and proposed correspondence
Middle LiFePO
4And FePO
4Two-phase changes the electrical conduction mechanism of the p-n junction transformation that takes place; Shi.S.Q., Chen, L.Q. etc. (physical comment B, Physical TRview B, 68 volumes, 19 phases, 195108-1 page) utilization first principle has calculated the trace Cr Li doped
1-3xCr
xFePO
4Density of electronic states, fermi level, the new electrical conduction mechanism based on the conduction tunnel of dopant ion 3d energy level and Fe, O energy level hydridization has been proposed; Hu, Y.Q., Doeff, M.M., Kostecki, R., Finones, R. (electrochemistry journal, Journal of theElectrochemical Society, 151 volumes, 8 phases, A1279 page or leaf) uses sol-gel processing to prepare adulterated Li first
0.98Mg
0.01FePO
4And Li
0.96Ti
0.01FePO
4Positive electrode material has improved LiFePO equally
4The base batteries performance; Ni, J.F. etc. (material wall bulletin, Materials Letters, 59 volumes, 18 phases, 2361 pages) utilization coprecipitation method has prepared mixes Mg
2+, Cu
2+, Zn
2+LiFePO
4Positive pole powder discharges under the C/10 multiplying power, obtains the above capacity of 120mAh/g.Mention compound in the U.S. Pat 2004005265 and consist of A
x(M '
1-aM "
a)
y(XD
4)
z, its M " and be doped element, 0.0001＜a≤0.1 has comprised IIA～VIIIA, IB ~ VIB element, but does not mention with VIIB and the 8th VIII of family as doped element; Though mention the transition metal that M ' relates to first transition system, they are the status as principal element rather than doped element.Whether these morphogenetic crystalline structure that mix have the character of slotting lithium-storage lithium on the other hand, also do not have checking and the support of embodiment as feasibility in this patent.And in this patent, more do not mention about thought and example in A position doping transition element.In a word, up to now, relevant transition element (not comprising the Fe element) is to iron lithium phosphate LiFePO
4Doping vario-property effect research in the lithium position does not appear in the newspapers as yet.
(be designated as TR) compound is a doped raw material to the present invention's proposition down together, utilizes conventional solid-state method to prepare transition element lithium position doped iron phosphate lithium Li with the transition element VIIB Mn of family, the 8th VIIICo of family, Ni
1-xTR
xFePO
4(0＜x≤0.05) has improved iron lithium phosphate LiFePO
4The base batteries performance of positive electrode material makes it have higher charge/discharge capacity and good cycle performance of battery.
Summary of the invention
The object of the present invention is to provide compound by the transition element VIIB Mn of family, the 8th VIIICo of family, Ni to iron lithium phosphate LiFePO
4In the lithium position carry out doping vario-property, significantly improve the preparation method of a kind of transition element doped type LiFePO 4 powder of the anode material for lithium ion battery of parent base batteries performance.It is characterized in that described lithium ion battery anode material lithium iron phosphate molecular formula Li
1-xTR
xFePO
4Expression, wherein TR is the doped source element, 0＜x≤0.05.
Concrete preparation method is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and transition element doped thing are pressed atomic ratio Li:Fe:P:TR=(1-x): batch mixing of the mol ratio of 1:1:x, added mix grinding medium mixing and ball milling 6～12 hours, after drying under 40～70 ℃, under inert atmosphere or reducing atmosphere, heat 400～550 ℃, be incubated 5～10 hours and carry out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtained transition element doped iron lithium phosphate Li then
1-xTR
xFePO
4Powder.
Described blending agent is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described hotchpotch is at least a in oxide compound, oxyhydroxide, muriate, nitrate, vitriol, carbonate and the organic salt of the transition element VIIB Mn of family, the 8th VIIICo of family, Ni.
Described lithium salts is Li
2CO
3, LiOH, lithium oxalate, at least a in Lithium Acetate and the lithium nitrate.
Described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
Described phosphoric acid salt comprises in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate at least a.
Described inert atmosphere or reducing atmosphere are nitrogen, at least a in argon gas and the nitrogen and hydrogen mixture.
The invention has the beneficial effects as follows and utilize the solid phase method that is easy to commercially produce, the draw materials compound of the various widely transition element VIIB Mn of family, the 8th VIIICo of family, Ni of doping, through the simple stoving process that mixes, by control thermal treatment temp and time, it is good to prepare crystal property, composition is even, transition element doped anode material for lithium ion battery iron lithium phosphate Li
1-xTR
xFePO
4(0＜x≤0.05) powder, first discharge specific capacity is 50-110mAh/g under the room temperature.Compare with other metallic cation doping routes, the present invention can significantly improve parent base batteries capacity and capacity cycle performance more, has clear superiority, and is very with practical value, has wide application prospect at secondary lithium battery, particularly power source commonly used with the cell positive material field.
Embodiment
The invention provides compound by the transition element VIIB Mn of family, the 8th VIIICo of family, Ni to LiFePO
4In the lithium position mix, significantly improve a kind of preparation method of transition element doped iron lithium phosphate powder of the anode material for lithium ion battery of parent base batteries performance.Described lithium ion battery anode material lithium iron phosphate molecular formula Li
1-xTR
xFePO
4Expression, wherein TR is the doped source element, 0＜x≤0.05;
It is as follows that described transition element is mixed the concrete preparation method side of LiFePO 4 powder:
Lithium salts, ferrous salt and phosphoric acid salt and transition element doped thing are pressed atomic ratio Li:Fe:P:TR=, and (1-x): the mol ratio of 1:1:x is once reinforced, add at least a in deionized water, industrial spirit and the dehydrated alcohol then as the mix grinding medium, mixing and ball milling 6～12 hours, 40～70 ℃ of oven dry; Oven dry back powder heats 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 5～10 hours and carry out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtained transition element doped iron lithium phosphate Li then
1-xTR
xFePO
4Powder.
Described hotchpotch is at least a in oxide compound, oxyhydroxide, muriate, nitrate, vitriol, carbonate and the organic salt of the transition element VIIB Mn of family, the 8th VIIICo of family, Ni.
Described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate, Lithium Acetate and the lithium nitrate.
Described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
Described phosphoric acid salt comprises in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate at least a.
Described blending agent is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described inert atmosphere or reducing atmosphere are at least a in nitrogen, argon gas and the nitrogen and hydrogen mixture.
With transition element doped iron lithium phosphate and conductive carbon black, polyvinylidene difluoride (PVDF), by (9～16): (0.875～2.2): 1 mass ratio is coated on the collector aluminium flake after grinding evenly, makes electrode slice, is negative pole with the metal lithium sheet, with the LiPF of 1.0mol/L
6Being dissolved in the ethyl-carbonate of volume ratio 1:1 and the mixed solvent of methylcarbonate is electrolytic solution, and polypropylene microporous film is a barrier film, is assembled into the simulation Li-Ion rechargeable battery.
The system of discharging and recharging of the respective battery of described assembling is: press 0.05-0.2C multiplying power constant current charge-discharge under the 2.5V-4.2V stopping potential.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
With 0.0997 moles of hydrogen Lithium Oxide 98min LiOHH
2O, 0.1 mole of Ferrox Fe (C
2O
4) 2H
2O and 0.1 mole of phosphoric acid ammonium dihydrogen NH
4H
2PO
4With 0.0003 mole of four water cobalt oxalate Co (C
2O
4) 4H
2O mixes, add in the polyester jar, add the 70m1 raw spirit, mixed 10 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit is medium ball milling 6 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, be incubated 8 hours, be cooled to room temperature with stove, gained positive electrode material Li
0.997Co
0.003FePO
4
Take by weighing the 0.9g positive powder, add the 0.19g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1:1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours charges to 4.2 volts by the speed of 20mA/g (in positive pole), is discharged to 2.5 volts, and reversible first specific discharge capacity is about 89mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 70mAh/g.
Embodiment 2
With 0.0495 mole of Quilonum Retard Li
2CO
3, the ferrous Fe (CH of 0.1 molar acetate
3COO)
22H
2O and 0.1 mole of phosphoric acid ammonium (NH
4)
3PO
4Mix with 0.001 mole of cobalt oxide CoO, add in the polyester jar, add the 100ml industrial spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 430 ℃ with 5 ℃/minute temperature rise rates, be incubated 7.5 hours, cool to room temperature with the furnace, obtain pre-imitation frosted glass, with water is medium ball milling 10 hours, O.3 discharging oven dry back rising/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9:1, volume ratio) under, rise to 720 ℃ with 4 ℃/minute temperature rise rates, be incubated 7 hours, be cooled to room temperature, obtain positive electrode material Li with stove
0.99Co
0.01FePO
4
Take by weighing the 1.125g positive powder, add the 0.169g carbon black, the 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible first specific discharge capacity that obtains battery is about 79mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 70mAh/g.
Embodiment 3
With 0.098 molar acetate lithium Li (CH
3COO, 0.1 mole of iron protochloride FeCl
2And 0.1 mole of phosphoric acid hydrogen, two ammonium (NH
4)
2HPO
4With 0.002 mole of CoCL2 CoCl
26H
2O mixes, add in the polyester jar, add the 75ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 450 ℃ with 5 ℃/minute temperature rise rates, be incubated 9 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit is medium ball milling 10 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.98Co
0.02FePO
4
Take by weighing the 1.02g positive powder, add the 0.184g carbon black, the 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible first specific discharge capacity that obtains battery is about 110mAh/g.Through 20 circulations, specific discharge capacity remains on more than the 100mAh/g.
Embodiment 4
With 0.048 mole of Quilonum Retard, the ferrous FeSO of 0.1 mol sulfuric acid
47H
2O and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.004 mole of heptahydrate CoSO
47H
2O mixes, add in the polyester jar, add the 100ml raw spirit, mixed 11 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 480 ℃ with 5 ℃/minute temperature rise rates, be incubated 5 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water is medium ball milling 5 hours, discharging oven dry back rose to 680 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 11 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.96Co
0.04FePO
4
Take by weighing the 0.9g positive powder, add the 0.16g carbon black, the 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 105mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 90mAh/g.
Embodiment 5
With 0.0995 molar nitric acid lithium, 0.1 mole of iron protochloride and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0005 mole of six water manganous nitrate Mn (NO
3)
26H
2O mixes, add in the polyester jar, add the 55ml industrial spirit, mixed 6.5 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8.5 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 5.5 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.995Mn
0.005FePO
4
Take by weighing the 0.537g positive powder, add the 0.066g carbon black, the 0.036g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 80mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 75mAh/g.
Embodiment 6
With 0.0495 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium and 0.001 mole of manganous carbonate MnCO
3Mix, add in the polyester jar, add 130ml water, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, cool to room temperature with the furnace, obtain pre-imitation frosted glass, with water is medium ball milling 8 hours, and discharging oven dry back is under 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9:1, volume ratio), rise to 700 ℃ with 4 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.99Mn
0.01FePO
4
Take by weighing the 1.325g positive powder, add the 0.263g carbon black, the 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 10mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 53mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 50mAh/g.
Embodiment 7
With 0.0976 molar acetate lithium, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0024 mole of oxalic acid dihydrate manganese Mn (C
2O
4) 2H
2O mixes, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water is medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.976Mn
0.024FePO
4
Take by weighing the 0.45g positive powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 69mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 60mAh/g.
Embodiment 8
With 0.095 moles of hydrogen Lithium Oxide 98min, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.005 mole of manganese oxide (MnO
2) mix, add in the polyester jar, add the 60ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 420 ℃ with 5 ℃/minute temperature rise rates, be incubated 9 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with the industrial spirit be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 3 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 7 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.95Mn
0.05FePO
4
Take by weighing the 0.45g positive powder, add the 0.0448g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 81mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 65mAh/g.
Embodiment 9
With 0.0999 molar nitric acid lithium LiNO
3, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0001 mole of six water nitric acid nickel (NO
3)
26H
2O mixes, add in the polyester jar, add the 60ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 6 hours, discharging oven dry back rose to 750 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.999Ni
0.001FePO
4
Take by weighing the 0.45g positive powder, add the 0.06g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 25mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 60mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 42mAh/g.
Embodiment 10
With 0.0995 molar acetate lithium, 0.1 molar acetate is ferrous and 0.1 mole of phosphoric acid ammonium and 0.0005 mole of oxidation nickel O mixing, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.995Ni
0.005FePO
4
Take by weighing the 0.45g positive powder, add the 0.078g carbon black, the 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 30mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 57mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 44mAh/g.
Embodiment 11
With 0.04925 mole of Quilonum Retard, 0.1 mole of iron protochloride and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.0015 mole of nickelous carbonate NiCO
3Mix, add in the polyester jar, add the 80ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain pre-imitation frosted glass, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.985Ni
0.015FePO
4
Take by weighing the 0.843g positive powder, add the 0.078g carbon black, the 0.062g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 40mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 73mAh/g of battery.Through 20 circulations, the specific discharge capacity that respective material shows remains on more than the 45mAh/g.
Embodiment 12
With 0.097 moles of hydrogen Lithium Oxide 98min, 0.1 mole of Ferrox and 0.1 mole of phosphoric acid hydrogen, two ammoniums and 0.003 moles of hydrogen oxidation nickel (OH)
2Mix, add in the polyester jar, add the 50ml water-alcohol, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove, with water be medium ball milling 6 hours, discharging oven dry back rose to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
0.97Ni
0.03FePO
4
Take by weighing the 0.624g positive powder, add the 0.09g carbon black, the 0.052g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 20mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, obtains the reversible first specific discharge capacity 78mAh/g of battery.Through 20 circulations, the specific discharge capacity that shows remains on more than the 55mAh/g.
Claims (5)
1. the preparation method of a transition element doped iron lithium phosphate powder is characterized in that, transition element doped iron lithium phosphate Li
1-xTR
xFePO
4Expression, wherein 0＜x≤0.05; TR is a doped source,
Concrete preparation method is as follows:
Transition element doped thing is pressed atomic ratio Li:Fe:P:TR=, and (1-x): the mol ratio of 1:1:x and lithium salts, ferrous salt and weighing charging of phosphoric acid salt add the mix grinding medium, 6～12 hours ball milling time, oven dry under 40～70 ℃; Oven dry back powder is heated to 400～550 ℃ under inert atmosphere or reducing atmosphere, be incubated 5～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtain transition element doped iron lithium phosphate Li then
1 -xTR
xFePO
4Powder; Wherein the mix grinding medium is a kind of in raw spirit, industrial spirit and the water; Described hotchpotch is at least a in oxide compound, oxyhydroxide, muriate, nitrate, vitriol and the organic salt of above-mentioned three kinds of elements of the transition element VIIB Mn of family and the Co of VIII family, Ni.
2. according to the preparation method of the described transition element doped iron lithium phosphate powder of claim 1, it is characterized in that described lithium salts is at least a in lithium oxalate, Lithium Acetate and the lithium nitrate.
3. according to the preparation method of the described transition element doped iron lithium phosphate powder of claim 2, it is characterized in that described lithium salts substitutes with LiOH.
4. according to the preparation method of the described transition element doped iron lithium phosphate powder of claim 1, it is characterized in that described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
5. according to the preparation method of the described transition element doped iron lithium phosphate powder of claim 1, it is characterized in that described phosphoric acid salt is at least a in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate.
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| CN101332985B (en) * | 2008-07-31 | 2011-05-04 | 福建师范大学 | Method for preparing conducting phosphide-doped positive electrode material of LiFePO4 |
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| 镁离子掺杂对LiFePO4/C材料电池性能的影响. 卢俊彪等.物理化学学报，第21卷第3期. 2005 * |
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