CN103022487B - A kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery - Google Patents
A kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery Download PDFInfo
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- CN103022487B CN103022487B CN201210557982.5A CN201210557982A CN103022487B CN 103022487 B CN103022487 B CN 103022487B CN 201210557982 A CN201210557982 A CN 201210557982A CN 103022487 B CN103022487 B CN 103022487B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 16
- 229920000053 polysorbate 80 Polymers 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 150000001722 carbon compounds Chemical class 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 12
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 12
- 229940113124 polysorbate 60 Drugs 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- -1 hydrocarbon oxygen compound Chemical class 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- 229920001219 Polysorbate 40 Polymers 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- 229940093474 manganese carbonate Drugs 0.000 claims description 6
- 235000006748 manganese carbonate Nutrition 0.000 claims description 6
- 239000011656 manganese carbonate Substances 0.000 claims description 6
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 claims description 6
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 claims description 6
- 229940101027 polysorbate 40 Drugs 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 description 12
- 238000010583 slow cooling Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 11
- 240000002609 Pyrus pyrifolia var. culta Species 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 238000005303 weighing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method 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
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery, belong to anode material of lithium battery technical field.Preparation method's first step in the present invention is mixed with precursor process in the liquid phase, raw material is mixed and reaches molecule, ionic level, the nonionic surface active agent added is conducive to the separation of raw material on the one hand, reducing atmosphere is provided on the other hand in follow-up roasting process, even particle distribution is obtained by two steps above, the manganese pyrophosphate material of pattern rule, is conducive to subsequent high temperature reaction preparation lithium manganese phosphate material.Simultaneously coated by the carbon of substep, be conducive to the electronic conductivity improving material.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, more particularly, the present invention relates to a kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery, belong to anode material of lithium battery technical field.
Background technology
Lithium rechargeable battery, as novel green battery, has developed quite rapid since appearance.Compared with the conventional secondary cell such as lead-acid battery, nickel-cadmium cell, Ni-MH battery, the unique advantage such as lithium rechargeable battery has that open circuit voltage is high, energy density is large, self-discharge rate is low, long service life, pollution-free and security performance are good, range of application is more and more extensive.
Cobalt acid lithium material also exists expensive raw material price, capacity as the commercial anode material for lithium-ion batteries of the first generation and has almost performed to the defects such as the limit, resource scarcity, poor stability.Exploitation energy density is large, and fail safe is good, and the positive electrode of cycle performance excellence is more and more important.The wherein LiMnPO of polyanion
4material has 170mAh/g theoretical specific capacity, and its charging and discharging curve is (4.1Vvs.Li very steadily
+/ Li).The advantages such as this material has raw material sources extensively simultaneously, environmental friendliness, and material structure is stablized, and cyclical stability is outstanding, are therefore considered to one of positive electrode of the energy-storage battery with larger future.
But the conductivity that this material is low and low lithium ion diffusion coefficient cause its high rate performance poor, thus greatly limit it and further apply.At present, both at home and abroad to raising LiMnPO
4high rate capability study widely, mainly deal with problems from following two aspects:
1, the ion doping of diverse location and Surface coating conductive phase is adopted to improve LiMnPO
4conductivity.Such as: it is 201010591316.4 that State Intellectual Property Office's Chinese patent discloses an application number in 2011.5.25, name is called the patent of invention of " synthetic method of lithium ion battery anode material manganese lithium phosphate/carbon ", this patent adopts solid phase method to prepare the composite material of lithium manganese phosphate and amorphous carbon, is improved the chemical property of material by the amorphous carbon of coated with conductive.But because the shape of initiation material is random, the material granule pattern of Solid phase synthesis is difficult to control, and particle size is comparatively large, material particle size skewness, thus cause material high rate performance improvement effect and not obvious.
2, optimized fabrication technique, adopts different synthetic methods such as hydro thermal method, sol-gal process and microwave method etc. to prepare the tiny LiMnPO of particle
4material, by reducing particle size to shorten the migration distance of electronics and lithium ion, thus improves the conductivity of material.Such as: the people such as DelacourtC (One-steplow-temperaturerouteforthepreparationofelectroch emicallyactiveLiMnPO4powders.ChemMater, 2004,16:93-99) prepare the LiMnPO of size at about 100nm by liquid-phase precipitation method
4particle, its reversible capacity has brought up to 70mAh/g by the 35mAh/g of 1um particle diameter.Relatively-high temperature solid phase method liquid phase method has the advantage raw material that hardly matches to be blended in intermolecular carrying out, and synthesis temperature is low, and product grain fine size is even, and size distribution ranges is narrow.And shortcoming is: synthesis condition is relatively harsh, lithium source consumes more, complicated process of preparation difficulty; The material crystalline degree of Liquid preparation methods is relatively low simultaneously, easily produces antistructure defect.
Summary of the invention
The present invention is intended to solve the particle diameter that the preparation method of prior art is difficult to control material granule, domain size distribution is uneven, the problem of complicated process of preparation, provide a kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery, effectively can control particle diameter and the phase constituent of lithium manganese phosphate, improve its uniformity and electric conductivity, improve its chemical property.
A preparation method for nanometer manganese lithium phosphate anode material of lithium battery, is characterized in that: comprise following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.005-0.1 weigh, dissolve in deionized water, regulate the pH value of solution to be 1-6 by ammoniacal liquor simultaneously, at 50-80 DEG C, obtain the slurry of solid content at 80-90% after stirring reaction;
B, slurry steps A obtained are placed in the inert atmosphere roasting 6-24 hour of 450-750 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1-1.05:1:0.01-0.4 in the mol ratio of lithium, manganese, carbon weighs, be dissolved in deionized water and make its solid content be 20-60%, after ball milling mixes, spraying dry, obtains powder body material;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and at 500-850 DEG C of roasting temperature 6-24 hour, cooling obtains nanometer manganese lithium phosphate anode material of lithium battery naturally.
Preferably, in step, described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound in the present invention.
Preferably, in step, described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate in the present invention.
Preferably, in step, described nonionic surface active agent is poly yamanashi esters nonionic surface active agent in the present invention.
Further, described poly yamanashi esters nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40.
Preferably, in step, the time of described stirring reaction is 6-12 hour in the present invention.
Preferably, the present invention is in step C, and described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
Preferably, the present invention is in step C, and described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
Multiple as: a kind of or arbitrary proportion in poly yamanashi esters, soluble starch, tartaric acid, polypropylene, polyvinyl alcohol of above-mentioned routine.
Preferably, the present invention is in step C, and described Ball-milling Time is 6-10 hour.
Preferably, the present invention is in step C, and it is 180-280 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 100-150 DEG C.
The Advantageous Effects that the present invention brings:
1, the nanometer manganese lithium phosphate anode material of lithium battery particle fine particle size prepared by preparation method of the present invention is evenly distributed, pattern rule, Stability Analysis of Structures, removal lithium embedded invertibity is good, high rate performance is excellent, and this preparation technology is simple simultaneously, easy to control, raw material sources are extensive, easily realize industrialization;
2, the preparation method's first step in the present invention is mixed with precursor process in the liquid phase, raw material is mixed and reaches molecule, ionic level, the nonionic surface active agent added is conducive to the separation of raw material on the one hand, reducing atmosphere is provided on the other hand in follow-up roasting process, even particle distribution is obtained by two steps above, the manganese pyrophosphate material of pattern rule, is conducive to subsequent high temperature reaction preparation lithium manganese phosphate material.Simultaneously coated by the carbon of substep, be conducive to the electronic conductivity improving material;
3, method preparation technology of the present invention is simple, and product purity is high, and chemical property is good, and be easy to suitability for industrialized production, preferred Ball-milling Time and spray drying parameters both improve production efficiency, can ensure again the quality of final product.
Accompanying drawing explanation
The lithium manganese phosphate material of Fig. 1 prepared by embodiment 9 and embodiment 10 discharge curve of (1C=170mAh/g) under 0.05C multiplying power, voltage range 2.5-4.5V, electrolyte is 1mol/LLiPF
6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, probe temperature is 25 DEG C ± 0.5 DEG C; Wherein a, b curve is respectively the discharge curve of lithium manganese phosphate material in embodiment 9 and embodiment 10.
Embodiment
embodiment 1
A preparation method for nanometer manganese lithium phosphate anode material of lithium battery, comprises following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.005 weigh, dissolve in deionized water, regulate the pH value of solution to be 1 by ammoniacal liquor simultaneously, obtain after stirring reaction at 50 DEG C solid content 80% slurry;
B, slurry steps A obtained are placed in the inert atmosphere roasting 6 hours of 450 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1:1:0.01 in the mol ratio of lithium, manganese, carbon weighs, and is dissolved in deionized water and makes its solid content be 20%, after ball milling mixes, spraying dry, obtains powder body material;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and 500 DEG C of roasting temperatures 6 hours, cooling obtained nanometer manganese lithium phosphate anode material of lithium battery naturally.
embodiment 2
A preparation method for nanometer manganese lithium phosphate anode material of lithium battery, comprises following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.1 weigh, dissolve in deionized water, regulate the pH value of solution to be 6 by ammoniacal liquor simultaneously, obtain after stirring reaction at 80 DEG C solid content 90% slurry;
B, slurry steps A obtained are placed in the inert atmosphere roasting 24 hours of 750 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1.05:1:0.4 in the mol ratio of lithium, manganese, carbon weighs, and is dissolved in deionized water and makes its solid content be 60%, after ball milling mixes, spraying dry, obtains powder body material;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and 850 DEG C of roasting temperatures 24 hours, cooling obtained nanometer manganese lithium phosphate anode material of lithium battery naturally.
embodiment 3
A preparation method for nanometer manganese lithium phosphate anode material of lithium battery, comprises following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.0525 weigh, dissolve in deionized water, regulate the pH value of solution to be 3.5 by ammoniacal liquor simultaneously, obtain after stirring reaction at 65 DEG C solid content 85% slurry;
B, slurry steps A obtained are placed in the inert atmosphere roasting 15 hours of 600 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1.025:1:0.205 in the mol ratio of lithium, manganese, carbon weighs, and is dissolved in deionized water and makes its solid content be 40%, after ball milling mixes, spraying dry, obtains powder body material;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and 675 DEG C of roasting temperatures 15 hours, cooling obtained nanometer manganese lithium phosphate anode material of lithium battery naturally.
embodiment 4
A preparation method for nanometer manganese lithium phosphate anode material of lithium battery, comprises following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.086 weigh, dissolve in deionized water, regulate the pH value of solution to be 5 by ammoniacal liquor simultaneously, obtain after stirring reaction at 79 DEG C solid content 81% slurry;
B, slurry steps A obtained are placed in the inert atmosphere roasting 21 hours of 720 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1.01:1:0.33 in the mol ratio of lithium, manganese, carbon weighs, and is dissolved in deionized water and makes its solid content be 56%, after ball milling mixes, spraying dry, obtains powder body material;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and 517 DEG C of roasting temperatures 8 hours, cooling obtained nanometer manganese lithium phosphate anode material of lithium battery naturally.
embodiment 5
On the basis of embodiment 1-4:
Preferably, in step, described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound.
Preferably, in step, described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
Preferably, in step, described nonionic surface active agent is poly yamanashi esters nonionic surface active agent.
Further, described poly yamanashi esters nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40.
Preferably, in step, the time of described stirring reaction is 6 hours.
Preferably, in step C, described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
Preferably, in step C, described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
Preferably, in step C, described Ball-milling Time is 6 hours.
Preferably, in step C, it is 180 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 100 DEG C.
embodiment 6
On the basis of embodiment 1-4:
Preferably, in step, described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound.
Preferably, in step, described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
Preferably, in step, described nonionic surface active agent is poly yamanashi esters nonionic surface active agent.
Further, described poly yamanashi esters nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40.
Preferably, in step, the time of described stirring reaction is 12 hours.
Preferably, in step C, described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
Preferably, in step C, described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
Preferably, in step C, described Ball-milling Time is 10 hours.
Preferably, in step C, it is 280 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 150 DEG C.
embodiment 7
On the basis of embodiment 1-4:
Preferably, in step, described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound.
Preferably, in step, described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
Preferably, in step, described nonionic surface active agent is poly yamanashi esters nonionic surface active agent.
Further, described poly yamanashi esters nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40.
Preferably, in step, the time of described stirring reaction is 9 hours.
Preferably, in step C, described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
Preferably, in step C, described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
Preferably, in step C, described Ball-milling Time is 8 hours.
Preferably, in step C, it is 230 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 125 DEG C.
embodiment 8
On the basis of embodiment 1-4:
Preferably, in step, described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound.
Preferably, in step, described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
Preferably, in step, described nonionic surface active agent is poly yamanashi esters nonionic surface active agent.
Further, described poly yamanashi esters nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40.
Preferably, in step, the time of described stirring reaction is 11 hours.
Preferably, in step C, described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
Preferably, in step C, described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
Preferably, in step C, described Ball-milling Time is 7.5 hours.
Preferably, in step C, it is 199 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 137 DEG C.
embodiment 9
Respectively with NH
4h
2pO
4, Mn (CH
3cOO)
2for phosphorus source, manganese source, take Tween 80 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.02 of phosphorus, manganese, Tween 80, be dissolved in deionized water, regulate the pH value of solution to be 2 by ammoniacal liquor simultaneously, at 80 DEG C of temperature stirring reaction obtain after 6 hours solid content 90% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 450 DEG C of constant temperature calcinings after 24 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 30-50nm.
By manganese pyrophosphate, lithium hydroxide, tartaric acid (be wherein lithium source with lithium hydroxide, tartaric acid be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1.02:1:0.05 of lithium, manganese, carbon source makes its solid content be 40%, after ball milling mixes for 6 hours, be 250 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 120 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 600 DEG C of constant temperature calcinings after 6 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 50-80nm.
Electrode is made as follows by the lithium manganese phosphate material of above-mentioned gained.
With organic solvent 1-methyl-2 pyrrolidones (NMP) for solvent, after the electrode material, conductive agent (acetylene black) and the binding agent Kynoar (PVDF) that prepare in mass ratio 75:15:10 mixing and stirring, be evenly coated in the aluminum foil current collector that diameter is 14mm, 75 DEG C of oven dry in drying box, then tablet press machine compacting is used evenly, obtained electrode slice to be measured.Button type simulated battery is adopted to carry out battery assembling to prepared electrode slice.Be wherein metal lithium sheet to electrode, barrier film is Celgard2325 composite membrane, and electrolyte is 1mol/L.
LiPF
6equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, battery pack is contained in the glove box being full of argon gas and completes.Constant current charge-discharge test is done between 2.5-4.5V voltage range to filled battery.Under its 0.05C multiplying power, the discharge curve of (1C=170mAh/g) is as shown in a in Fig. 1 of Figure of description.
embodiment 10
Respectively with NH
4h
2pO
4, MnO
2for phosphorus source, manganese source, take Tween 80 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.005 of phosphorus, manganese, Tween 80, be dissolved in deionized water, regulate the pH value of solution to be 6 by ammoniacal liquor simultaneously, at 60 DEG C of temperature stirring reaction one section obtain after 10 hours solid content 80% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 550 DEG C of constant temperature calcinings after 20 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 40-60nm.
By manganese pyrophosphate, lithium hydroxide, polyvinyl alcohol (be wherein lithium source with lithium hydroxide, polyvinyl alcohol be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1.03:1:0.01 of lithium, manganese, carbon source makes its solid content be 60%, after ball milling mixes for 8 hours, be 180 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 100 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 650 DEG C of constant temperature calcinings after 10 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 60-90nm.
embodiment 11
Respectively with (NH
4)
2hPO
4, MnCO
3for phosphorus source, manganese source, take polysorbate60 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.001 of phosphorus, manganese, polysorbate60, be dissolved in deionized water, regulate the pH value of solution to be 1 by ammoniacal liquor simultaneously, at 70 DEG C of temperature stirring reaction obtain after 8 hours solid content 85% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 700 DEG C of constant temperature calcinings after 10 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 30-60nm.
By manganese pyrophosphate, lithium carbonate, polyvinyl alcohol (be wherein lithium source with lithium carbonate, polyvinyl alcohol be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1:1:0.1 of lithium, manganese, carbon source makes its solid content be 20%, after ball milling mixes for 10 hours, be 280 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 150 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 750 DEG C of constant temperature calcinings after 10 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 80-110nm.
embodiment 12
Respectively with (NH
4)
2hPO
4, Mn (OH)
2for phosphorus source, manganese source, take polysorbate60 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.1 of phosphorus, manganese, polysorbate60, be dissolved in deionized water, regulate the pH value of solution to be 3 by ammoniacal liquor simultaneously, obtain after stirring reaction a period of time at 60 DEG C of temperature solid content 85% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 600 DEG C of constant temperature calcinings after 6 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 30-60nm.
By manganese pyrophosphate, lithium acetate, soluble starch (be wherein lithium source with lithium acetate, soluble starch be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1.05:1:0.4 of lithium, manganese, carbon source makes its solid content be 50%, after ball milling mixes for 10 hours, be 240 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 110 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 850 DEG C of constant temperature calcinings after 6 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 80-120nm.
embodiment 13
Respectively with (NH
4)
3pO
4, Mn (CH
3cOO)
2for phosphorus source, manganese source, take Tween 80 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.05 of phosphorus, manganese, polysorbate60, be dissolved in deionized water, regulate the pH value of solution to be 4 by ammoniacal liquor simultaneously, at 60 DEG C of temperature stirring reaction obtain after 10 hours solid content 80% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 750 DEG C of constant temperature calcinings after 6 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 40-80nm.
By manganese pyrophosphate, lithium acetate, Tween 80 (be wherein lithium source with lithium acetate, Tween 80 be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1.02:1:0.2 of lithium, manganese, carbon source makes its solid content be 40%, after ball milling mixes for 10 hours, be 250 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 140 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 750 DEG C of constant temperature calcinings after 12 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 70-110nm.
embodiment 14
Respectively with NH
4h
2pO
4, MnCO
3for phosphorus source, manganese source, take Tween 80 as surfactant.Weigh in the ratio of the stoichiometric proportion 1:1:0.005 of phosphorus, manganese, polysorbate60, be dissolved in deionized water, regulate the pH value of solution to be 3 by ammoniacal liquor simultaneously, at 50 DEG C of temperature stirring reaction obtain after 12 hours solid content 80% slurry; Prepared slurry is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 450 DEG C of constant temperature calcinings after 24 hours in stove slow cooling to room temperature obtain the manganese pyrophosphate powder of grey black, its particle size is 50-80nm.
By manganese pyrophosphate, lithium acetate, Tween 80 (be wherein lithium source with lithium acetate, Tween 80 be carbon source), weighing to be dissolved in deionized water in the ratio of the stoichiometric proportion 1.05:1:0.2 of lithium, manganese, carbon source makes its solid content be 20%, after ball milling mixes for 10 hours, be 280 DEG C in inlet temperature, leaving air temp is carry out the precursor powder that spraying dry obtains grey black under the condition of 150 DEG C.Finally obtained powder is placed in tube furnace at N
2under protection with 5 DEG C/min be warming up to 500 DEG C of constant temperature calcinings after 24 hours in stove slow cooling to room temperature obtain the nanometer LiMnPO of grey black
4/ C powder, its particle size is 70-100nm.
Claims (5)
1. a preparation method for nanometer manganese lithium phosphate anode material of lithium battery, is characterized in that: comprise following processing step:
A, by containing manganese inorganic salts, phosphorous acid group inorganic salts and nonionic surface active agent by the mol ratio of manganese, phosphorus, nonionic surface active agent be 1:1:0.005 weigh, dissolve in deionized water, regulate the pH value of solution to be 1 by ammoniacal liquor simultaneously, at 50 DEG C stirring reaction obtain after 6 hours solid content 80% slurry; Described nonionic surface active agent is the multiple of a kind of or arbitrary proportion in Tween 80, polysorbate60 and polysorbate40;
B, slurry steps A obtained are placed in the inert atmosphere roasting 6 hours of 450 DEG C, and cooling obtains nanometer manganese pyrophosphate material naturally;
C, by the nanometer manganese pyrophosphate material of gained in step B and lithium-containing compound, carbon compound, the ratio being 1:1:0.01 in the mol ratio of lithium, manganese, carbon weighs, and is dissolved in deionized water and makes its solid content be 20%, after ball milling mixes, spraying dry, obtains powder body material; Described Ball-milling Time is 6 hours; It is 180 DEG C that described spraying dry is specially inlet temperature, and leaving air temp is 100 DEG C;
D, the powder body material obtained by step C are placed in inert atmosphere protection stove, and 500 DEG C of roasting temperatures 6 hours, cooling obtained nanometer manganese lithium phosphate anode material of lithium battery naturally.
2. the preparation method of a kind of nanometer manganese lithium phosphate anode material of lithium battery according to claim 1, is characterized in that: in step, and described is manganese carbonate, manganese nitrate, manganese acetate or manganese oxalate containing manganese compound.
3. the preparation method of a kind of nanometer manganese lithium phosphate anode material of lithium battery according to claim 1, is characterized in that: in step, and described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
4. the preparation method of a kind of nanometer manganese lithium phosphate anode material of lithium battery according to claim 1, is characterized in that: in step C, and described lithium-containing compound is any one in lithium hydroxide, lithium oxalate, lithium acetate, lithium nitrate or lithium carbonate.
5. the preparation method of a kind of nanometer manganese lithium phosphate anode material of lithium battery according to claim 1, is characterized in that: in step C, and described carbon compound is the multiple of one or any ratio in hydrocarbon oxygen compound and hydrocarbon.
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