CN101369659B - Novel lithium iron phosphate anode material used for lithium ion battery and method of manufacturing the same - Google Patents
Novel lithium iron phosphate anode material used for lithium ion battery and method of manufacturing the same Download PDFInfo
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- CN101369659B CN101369659B CN2007100757929A CN200710075792A CN101369659B CN 101369659 B CN101369659 B CN 101369659B CN 2007100757929 A CN2007100757929 A CN 2007100757929A CN 200710075792 A CN200710075792 A CN 200710075792A CN 101369659 B CN101369659 B CN 101369659B
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims description 18
- 239000010405 anode material Substances 0.000 title abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 23
- 229910001416 lithium ion Inorganic materials 0.000 title description 23
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 239000010452 phosphate Substances 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 27
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 22
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910011570 LiFe 1-x Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940062993 ferrous oxalate Drugs 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 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
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000004087 circulation Effects 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005955 Ferric phosphate Substances 0.000 abstract 2
- 229940032958 ferric phosphate Drugs 0.000 abstract 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- SNDJGKIVHKOEHY-UHFFFAOYSA-M S(=S)(=O)(O)O.S[Na] Chemical compound S(=S)(=O)(O)O.S[Na] SNDJGKIVHKOEHY-UHFFFAOYSA-M 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- DLWACICVJAABNE-UHFFFAOYSA-N OS(O)(=O)=S.N.S Chemical compound OS(O)(=O)=S.N.S DLWACICVJAABNE-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LFRGFTOHRVORLB-UHFFFAOYSA-M [O-]S(O)(=O)=S.S.[K+] Chemical compound [O-]S(O)(=O)=S.S.[K+] LFRGFTOHRVORLB-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a novel ferric phosphate lithium anode material for lithium battery, the ferric potential and phosphate potential are partly substituted simultaneously, with a molecular formula of LiFe<1-x>M<x>P<1-y>S<y>O<4>, M represents sodium element or potassium element, S represents sulfur element, 0<x<=0.5, 0<y<=0.5. The invention also discloses preparation method of the anode material. With the ferric potential, phosphate potential being substituted simultaneously, the ferric phosphate lithium anode material has charge and discharge capacity of high multiplying power and excellent battery circulation performance.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of Novel lithium iron phosphate anode for lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, has the voltage height, and energy density is large, good cycle, and self discharge is little, memory-less effect, the wide many merits that waits of operating temperature range.Be widely used in mobile phone, notebook computer, electronic instrument, portable power tool, electric bicycle, weaponry etc.In electric automobile, also have good application prospect, become the emphasis that competitively research and develop countries in the world at present.
Positive electrode is an important component part of lithium ion battery, also is the key that determines performance of lithium ion battery.Main lithium ion anode material is LiCoO at present
2, LiNiO
2, LiMn
2O
4LiCoO
2Be at present unique on a large scale industrialization, business-like positive electrode, 90% above lithium ion battery adopts this material.But this material price is expensive, and toxicity is larger, has certain safety issue.LiNiO
2Cost is also high, although specific capacity is higher, and the preparation difficulty, there is larger potential safety hazard in poor heat stability.Spinelle LiMn
2O
4Cost is low, and fail safe is good, but specific capacity is low, and high temperature cyclic performance is poor.Therefore need to develop novel positive electrode satisfies the growing market demand.
In recent years based on Fe
3+/ Fe
2+The material of oxidation-reduction pair causes people's very big interest, particularly has the LiFePO4 (LiFePO of olivine crystal structure
4) become the most promising alternative positive electrode of recent research.
The LiFePO of olivine structural
4Stability Analysis of Structures, stable operating voltage, platform identity is good.Its high-temperature behavior and good cycle, theoretical specific capacity higher (170mAh/g), safety non-toxic, cost is low, and bulk effect is good when cooperating with carbon negative pole material as lithium ion anode material, and is good with most of electrolyte system compatibility.It has become the focus of domestic and international recent research.But the electron conduction of this material is poor, has greatly limited the application of this material.Have at present mainly containing about improving this material property method of raising of reported in literature: 1. mix or coated with conductive material with carbon element and the intergranular electronic conductivity of conductive metal particle raising fertile material on the surface; 2. mix micro-high volence metal ion and partly replace Li
+Electronic conductivity in the fertile material is improved in the position; 3. relatively large transition elements replaces the iron position, improves the ionic conductivity of material.But still can not satisfy the specific capacity of high power charging-discharging battery and the requirement of cycle performance with the material that these methods obtain.
Summary of the invention
Purpose of the present invention is exactly the problems referred to above for prior art, provides a kind of for Novel lithium iron phosphate anode lithium ion battery, that possess higher high power charging-discharging capacity and good cycle performance of battery.
Another object of the present invention is to provide the preparation method of above-mentioned Novel lithium iron phosphate anode.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of Novel lithium iron phosphate anode for lithium ion battery, the iron position of described LiFePO4 and phosphate potential are partly replaced simultaneously, and it has molecular formula LiFe
1-xM
xP
1-yS
yO
4, M represents sodium element or potassium element, S represents element sulphur, 0＜x≤0.5,0＜y≤0.5.
The invention also discloses the preparation method of above-mentioned Novel lithium iron phosphate anode, described method comprises step:
A, lithium salts, ferrous salt, phosphate and doped and substituted raw material are carried out batch mixing by following element molar ratio, Li:Fe:M:P:S=1:(1-x): x:(1-y): y, and add the mix grinding medium and carried out mixing and ball milling 2～12 hours, at least a in sodium thiosulfate, potassium thiosulfate or the ATS (Ammonium thiosulphate) that described doped and substituted raw material is ease of solubility;
B, under inert atmosphere, carried out precalcining 6～10 hours in 200～500 ℃;
C, under inert atmosphere, carried out secondary clacining 8～16 hours in 500～800 ℃.
Preferably, among the described step b, before precalcining with material ball milling 2～4 hours after 70～100 ℃ of oven dry.
Preferably, among the described step c, before secondary clacining, the material after the precalcining was carried out mixing and ball milling 2～10 hours, and the oven dry briquetting.
Described mix grinding medium is at least a in deionized water, industrial alcohol or the butanols.
Described lithium salts is at least a in lithium fluoride, lithium bromide, lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate.
Described ferrous salt is at least a in ferrous oxalate, the ferrous acetate.
Described phosphate is at least a in ammonium phosphate, diammonium hydrogen phosphate and the ammonium dihydrogen phosphate.
Described inert atmosphere is nitrogen, and is at least a in the argon gas.
Because adopted above scheme, the beneficial effect that the present invention is possessed is:
The invention provides simultaneously part substituted iron lithium phosphate material and preparation method thereof of a kind of iron position, phosphate potential, efficiently solve existing LiFePO4 (LiFePO
4) material during as the positive electrode of serondary lithium battery electronic conductivity and ionic conductivity low, adopt carbon coating and metal ion all can not reach the problem that the high magnification electric current discharges and recharges the requirement of battery in lithium position and the doping of iron position, iron of the present invention position, phosphate potential simultaneously part substituted iron lithium phosphate positive electrode possess higher high power charging-discharging capacity and good cycle performance of battery.
Preparation method's of the present invention advantage is: utilize the solid phase method that is easy to suitability for industrialized production, the doped and substituted thing is wide material sources, low-cost solubility thiosulfate, mix through simple mechanical ball milling, stoving process is by control heat treatment temperature and time, it is good to prepare crystal property, purity is high, homogeneous chemical composition, and iron position and phosphate potential are simultaneously by the part substituted iron lithium phosphate, its average grain diameter is 1～3 μ m, and the 5C specific discharge capacity can reach 105～120mAh/g under the room temperature.Advantage of the present invention also is to utilize the solubility thiosulfate to be the doped and substituted thing, make reaction mass reach easily the even mixing of molecular level ion level, solid phase synthesis process by maturation, can realize effectively replacing at parent phosphate potential and iron position, to improving LiFePO4 basis capacity and cycle electric performance obvious effect and advantage are arranged, at secondary lithium battery commonly used, particularly high magnification electric current power source has wide application prospect with the cell positive material field.
Embodiment
The invention provides with the sodium (Na in the thiosulfate
+), potassium (K
+) element partly replaces the iron in the LiFePO4, sulphur in the thiosulfate (S) part replaces the phosphorus in the LiFePO4, with a kind of iron position and the phosphate potential while part substituted iron lithium phosphate positive electrode that significantly improves parent base batteries performance, it can improve LiFePO4 basis battery performance, makes it possess higher high power charging-discharging capacity and good cycle performance of battery.Described lithium ion battery anode material lithium iron phosphate molecular formula LiFe
1-xM
xP
1-yS
yO
4Expression, wherein 0＜x≤0.5,0＜y≤0.5, M and S are substituted element.
LiFePO4 (LiFePO
4) mix the material that electricity is led as a kind of, in conduction electron, the solid electrolyte material of conductive lithium ion especially.In LiFePO4, transporting of lithium ion is at PO
4Transport in the passage that tetrahedron forms, the migration of lithium is subject to the impact of two aspects.The interactional impact that is subject to oxygen on the one hand.With after waiting mole monovalence metal to replace, because charge balance, will there be defective in the oxygen position in the iron position, and two monovalent atoms replace two ferrous iron atoms and produce an oxygen room.Work as PO
4In oxygen part defective form after, the Coulomb attraction that lithium ion is subject to reduces, the mobility of lithium ion in lattice can improve, thereby ionic conductivity also can improve, simultaneously oxygen part defective can improve the electronic conductivity of material; The lithium ion migration is subject to the impact of migrating channels size on the other hand.In LiFePO4, after phosphate potential replaced with the less sulphur atom of atomic radius, the lithium ion transport channel increased, and is beneficial to the lithium ion migration.Simultaneously, the sulphur (S of high price
6+) replace at a low price phosphorus (P5
+) be conducive to produce cation vacancy, be conducive to the lithium ion migration.
The present invention also proposes take thiosulfate as the doped and substituted raw material, utilizes solid phase method to prepare iron position and phosphate potential simultaneously by part substituted iron lithium phosphate LiFe
1-xM
xP
1-yS
yO
4The preparation method, wherein 0＜x≤0.5,0＜y≤0.5, M and S are substituted element.Concrete preparation method is as follows:
With lithium salts, ferrous salt, phosphate and doped and substituted thing are pressed element Li:Fe:M:P:S=1:(1-x): x:(1-y): the mol ratio Primary batching system of y is reinforced, then add deionized water, at least a as the mix grinding medium in industrial alcohol and the butanols, mixing and ball milling 2～12 hours, after 70～100 ℃ of lower oven dry, ball milling 2～4 hours, under inert atmosphere, be heated to 200～500 ℃, be incubated 6～10 hours and carry out precalcining, with Preburning material mixing and ball milling 2～10 hours, behind the oven dry briquetting, under inert atmosphere, be heated to 500～800 ℃, be incubated 8～16 hours, carry out secondary clacining, be down to room temperature with furnace temperature, after the pattern shaping, obtain simultaneously part substituted iron lithium phosphate powder LiFe of iron position and phosphate potential
1-xM
xP
1-yS
yO
4
Wherein, inert atmosphere can be nitrogen, and is at least a in the argon gas.
The doped and substituted thing is sodium thiosulfate, and is at least a in the potassium thiosulfate, and selects ATS (Ammonium thiosulphate) as mixing the sulphur substituent according to element proportioning needs.
Lithium salts is at least a in lithium fluoride, lithium bromide, lithium hydroxide, lithium carbonate, lithium oxalate, the lithium acetate.
Ferrous salt is at least a in ferrous oxalate, the ferrous acetate.
Phosphate comprises ammonium phosphate, diammonium hydrogen phosphate, and is at least a in the ammonium dihydrogen phosphate.
With LiFePO4 LiFe
1-xM
xP
1-yS
yO
4Powder and conductive carbon black, Kynoar (PVDF), 1-METHYLPYRROLIDONE (NMP) are done form slurry by the mass ratio of 100:8.8:8.8:95 and are evenly coated on the collector aluminium foil, make positive plate; Make negative plate take graphite as negative material, with 1.0M LiPF
6Ethyl carbonate (EC), dimethyl carbonate (DMC) (1:1 volume ratio) mixed liquor be electrolyte, polypropylene microporous film is barrier film, is assembled into lithium ion battery (063048S).
The respective battery of described assembling discharges and recharges under 2.0～4.0V voltage range by the 5C multiplying power and does the cycle performance of battery test.
Further illustrate outstanding feature of the present invention and marked improvement below by embodiment.
Embodiment 1
With 3 moles of lithium fluoride; 2.94 mole ferrous oxalate; 2.94 mole of phosphoric acid ammonium dihydrogen; 0.03 the molar sulphur sodium thiosulfate mixes; adding 1000ml deionized water and 30ml industrial alcohol, and ball milling after the sealing (600～800r/min) 8 hours, the rear ball millings (700r/min) of discharging oven dry under 100 ℃ 4 hours; the heating rate of 2 ℃/min is warming up to 360 ℃ under nitrogen protection; be incubated 6 hours, carry out precalcining, precalcining pellet mill (700r/min) was mixed 4 hours; behind the briquetting; the heating rate of 3 ℃/min is warming up to 700 ℃ under nitrogen protection, this temperature insulation 10 hours, is down to room temperature with furnace temperature; after the pattern shaping, obtain LiFe
0.98Na
0.02P
0.98S
0.02O
4The LiFePO 4 powder positive electrode is designated as sample A.
The chemical property of gained sample is measured as follows, takes by weighing 100g sample A (LiFe
0.98Na
0.02P
0.98S
0.02O
4) the iron phosphate lithium positive pole powder, adding 8.8g conductive carbon black joins Kynoar (PVDF) (8.8g) after mixing and 1-METHYLPYRROLIDONE (NMP) mixed liquor (95g) dilutes in the glue, makes it to stir, the furnishing slurry, evenly coat on the collector aluminium foil, after 80 ℃ of dryings, be cut into long 400mm, the sheet of wide 41mm, flatten at roll squeezer, make the about 180 μ m of thickness, compacted density is 2.0g/cm
3Battery anode slice; Take by weighing graphite 135g, acetylene black 2g, LA132 (aqueous binders) 40g (containing 6 dries), water 140g mixes, stirred 2 hours, the even cathode size of furnishing is coated on the copper foil of affluxion body equably, after 80 ℃ of dryings, be cut into long 440mm, the sheet of wide 42mm flattens at roll squeezer, make the about 120 μ m of thickness, compacted density is 1.4g/cm
3Negative plate.With positive plate and negative plate at 80 ℃ of dried case inner dryings of vacuum more than 12 hours, naturally after cooling off with vacuum tank, as backup electrode and measure positive plate resistance, ethyl carbonate (EC), carbon ester dimethyl ester (DMC) (volume ratio is 1:1) mixed liquor that electrolyte adopts; Polypropylene microporous film is barrier film; in the glove box of argon gas atmosphere, be packaged into 063048S type battery and measure its internal resistance; become 12 hours by normally changing into sequencing; speed by 5C charges to 4.0V; be discharged to 2.0V, recording the battery specific discharge capacity that circulates for the third time is 116mAh/g, through 30 circulations; specific discharge capacity is 115mAh/g, sees the simulated battery test chart.
Embodiment 2
With 3 moles of lithium fluoride, 2.94 moles of ferrous oxalates, 2.94 mole of phosphoric acid ammonium dihydrogens and 0.03 molar sulphur potassium thiosulfate mix, and all the other steps are identical with embodiment 1, obtain LiFe
0.98K
0.02P
0.98S
0.02O
4LiFePO 4 powder is designated as sample B.
Press embodiment 1 method, utilize sample B battery pole piece processed and measure positive plate resistance; Be assembled into battery and measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 113mAh/g, is 111mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Embodiment 3
With 3 moles of lithium fluoride, 2.88 moles of ferrous oxalates, 2.88 mole of phosphoric acid ammonium dihydrogens and 0.06 molar sulphur sodium thiosulfate mix, and all the other steps are identical with embodiment 1, obtain LiFe
0.96Na
0.04P
0.96S
0.04O
4LiFePO 4 powder is designated as sample C.
Press embodiment 1 method, utilize sample C battery pole piece processed and measure positive plate resistance; Be assembled into battery and measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 114mAh/g, is 112mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Embodiment 4
With 3 moles of lithium fluoride, 2.94 moles of ferrous oxalates, 2.88 mole of phosphoric acid ammonium dihydrogens, 0.03 molar sulphur sodium thiosulfate and 0.03 molar sulphur ammonium thiosulfate mix, and all the other steps are identical with embodiment 1, obtain LiFe
0.98Na
0.02P
0.96S
0.04O
4LiFePO 4 powder is designated as sample D.
Press embodiment 1 method, utilize sample D battery pole piece processed and measure positive plate resistance; Be assembled into battery and measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 115mAh/g, is 114mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Comparative example 1
With 3 moles of lithium fluoride; 2.94 mole ferrous oxalate; 2.94 mole of phosphoric acid ammonium dihydrogen and 0.03 molar sulphur sodium thiosulfate mix; add 1000ml deionized water and 30ml industrial alcohol; ball milling is (600～800r/min) 8 hours after the sealing; the rear ball millings (700r/min) of discharging oven dry under 100 ℃ 4 hours, the heating rate of 2 ℃/min is warming up to 400 ℃ under nitrogen protection, is incubated 4 hours; carry out precalcining; precalcining pellet mill (700r/min) was mixed 4 hours, and behind the briquetting, the heating rate of 3 ℃/min is warming up to 850 ℃ under nitrogen protection; this temperature insulation 6 hours; be down to room temperature with stove, after the pattern shaping, obtain LiFe
0.98Na
0.02P
0.98S
0.02O
4LiFePO 4 powder is designated as sample E.
Press embodiment 1 method, utilize sample E battery pole piece processed and measure positive plate resistance; Be assembled into battery and measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 88mAh/g, is 80mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Comparative example 2
Mix micro-high volence metal ion and partly replace LiFePO4 lithium position
With 2.94 moles of lithium fluoride, 3 moles of ferrous oxalates, 3 mole of phosphoric acid ammonium dihydrogens, 0.06 moles of hydrogen magnesium oxide mixes, and all the other steps are identical with embodiment 1, obtain Li
0.98Mg
0.02FePO
4The LiFePO 4 powder positive electrode is designated as sample F.
Press embodiment 1 method, utilize sample F battery pole piece processed and measure positive plate resistance; Be assembled into battery and measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 82mAh/g, is 69mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Comparative example 3
Transition elements partly replaces LiFePO4 iron position
With 3 moles of lithium fluoride, 2.94 moles of ferrous oxalates, 3 mole of phosphoric acid ammonium dihydrogens, 0.06 molar nitric acid nickel mixes, and all the other steps are identical with embodiment 1, obtain LiFePO4 LiFe
0.98Ni
0.02PO
4The powder positive electrode is designated as sample G.
Press embodiment 1 method, utilize sample G battery pole piece processed, measure positive plate resistance; Be assembled into battery, measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 80mAh/g, is 76mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
Comparative example 4
The LiFePO4 coated with carbon
With 3 moles of lithium fluoride, 3 moles of ferrous oxalates, 3 mole of phosphoric acid ammonium dihydrogens, 130g sucrose mixes, and all the other steps are identical with embodiment 1, obtain LiFePO4 LiFePO
4/ C
0.08The powder positive electrode is designated as sample H.
Press embodiment 1 method, utilize sample H battery pole piece processed, measure positive plate resistance; Be assembled into battery, measure the internal resistance of cell, charge to 4.0V with the speed of 5C, be discharged to 2.0V, obtaining the battery specific discharge capacity that circulates for the third time is 70mAh/g, is 63mAh/g through 30 circulation specific discharge capacities, sees the simulated battery test chart.
The simulated battery table with test results
Can find out that from the simulated battery table with test results iron position and phosphate potential while part substituted iron lithium phosphate positive electrode that the present invention is used for secondary lithium battery have the cycle performance of battery that higher specific capacity is become reconciled under powerful charge status.From anode sheet resistor and the internal resistance of cell, its electronic conductance and ionic conductivity all increase really.From the decay of battery, its cycle performance is also better.Can make the exceeding of the condition of precalcining and secondary clacining formed lithium iron phosphate positive material microstructure produce defective or subside and cause the lithium ion channel part to stop up, the property indices that makes this product is variation all.
Claims (8)
1. the preparation method of a lithium iron phosphate positive material, the iron position of described LiFePO4 and phosphate potential are partly replaced simultaneously, and it has molecular formula LiFe
1-xM
xP
1-yS
yO
4, described method comprises step:
A, lithium salts, ferrous salt, phosphate and doped and substituted raw material are carried out batch mixing by following element molar ratio, Li:Fe:M:P:S=1:(1-x): x:(1-y): y, and add the mix grinding medium and carried out mixing and ball milling 2～12 hours, described doped and substituted raw material is sodium thiosulfate or potassium thiosulfate;
B, under inert atmosphere, carried out precalcining 6～10 hours in 200～500 ℃;
C, under inert atmosphere, carried out secondary clacining 8～16 hours in 500～800 ℃;
Wherein M represents sodium element or potassium element, and S represents element sulphur, 0＜x≤0.5,0＜y≤0.5.
2. preparation method according to claim 1 is characterized in that: among the described step b, before precalcining with material ball milling 2～4 hours after 70～100 ℃ of oven dry.
3. preparation method according to claim 1 is characterized in that: among the described step c, before secondary clacining the material after the precalcining was carried out mixing and ball milling 2～10 hours, and dry briquetting.
4. the described preparation method of any one according to claim 1～3 is characterized in that: described mix grinding medium is at least a in deionized water, industrial alcohol or the butanols.
5. the described preparation method of any one according to claim 1～3 is characterized in that: described lithium salts is at least a in lithium fluoride, lithium bromide, lithium carbonate, lithium hydroxide, lithium oxalate or the lithium acetate.
6. the described preparation method of any one according to claim 1～3 is characterized in that: described ferrous salt is at least a in ferrous oxalate, the ferrous acetate.
7. the described preparation method of any one according to claim 1～3 is characterized in that: described phosphate is at least a in ammonium phosphate, diammonium hydrogen phosphate and the ammonium dihydrogen phosphate.
8. the described preparation method of any one according to claim 1～3, it is characterized in that: described inert atmosphere is nitrogen, at least a in the argon gas.
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| CN2007100757929A CN101369659B (en) | 2007-08-17 | 2007-08-17 | Novel lithium iron phosphate anode material used for lithium ion battery and method of manufacturing the same |
| HK09107142.3A HK1128066A1 (en) | 2007-08-17 | 2009-08-04 | Lithium ferric phosphate positive material used in lithium battery and preparation method thereof |
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| CN103346295B (en) * | 2013-07-11 | 2016-06-15 | 宁波晟腾新材料有限公司 | A kind of preparation method of multielement-doped lithium iron phosphate composite positive pole |
| CN104852045A (en) * | 2014-02-19 | 2015-08-19 | 河南科隆新能源有限公司 | Method for preparing spherical lithium iron phosphate with high polymer lattice dispersion technology |
| CN106549145A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping sulphur in lithium ion battery |
| CN106848311A (en) * | 2017-03-16 | 2017-06-13 | 河南工程学院 | A kind of preparation method of the sulfur doping modified phosphate iron lithium anode material of high power capacity |
| CN114835100B (en) * | 2022-04-26 | 2023-11-17 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
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|---|---|---|---|---|
| CN1785823A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of phosphorus position partly substituted iron lithium phosphate powder |
| CN1797823A (en) * | 2004-12-21 | 2006-07-05 | 中国科学院物理研究所 | Anode material lithium ferric phosphate containing oxygen vacancy in use for secondary battery of lithium ion, and application |
| CN1915804A (en) * | 2006-09-07 | 2007-02-21 | 上海交通大学 | Method for preparing composite material of carbon coated lithium ferrous phosphate through iron phosphate |
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|---|---|---|---|---|
| CN1797823A (en) * | 2004-12-21 | 2006-07-05 | 中国科学院物理研究所 | Anode material lithium ferric phosphate containing oxygen vacancy in use for secondary battery of lithium ion, and application |
| CN1785823A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of phosphorus position partly substituted iron lithium phosphate powder |
| CN1915804A (en) * | 2006-09-07 | 2007-02-21 | 上海交通大学 | Method for preparing composite material of carbon coated lithium ferrous phosphate through iron phosphate |
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