CN101673819B - Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate - Google Patents
Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate Download PDFInfo
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- CN101673819B CN101673819B CN2009100935639A CN200910093563A CN101673819B CN 101673819 B CN101673819 B CN 101673819B CN 2009100935639 A CN2009100935639 A CN 2009100935639A CN 200910093563 A CN200910093563 A CN 200910093563A CN 101673819 B CN101673819 B CN 101673819B
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- manganese
- lithium
- manganese phosphate
- phosphate
- carbon composite
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 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 65
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 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
- 238000003756 stirring Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- -1 Super P Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 12
- 239000011164 primary particle Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000000247 postprecipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 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)
Abstract
The invention discloses a method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate, belonging to the technical field of energy material, comprising the following steps: firstly, preparing active manganese phosphate (MnPO4), secondly mixing the active manganese phosphate with lithium source and adding carbon source, ball milling and spray drying the materials, conducting heat treatment on the dried powder in the presence of protective atmosphere, heating to 300-850 DEG C and roasting for 2-12 hours and naturally cooling to obtain the manganese lithium phosphate/carbon composite material. The preparation method has low cost and simple synthesis technology, is applied to industrial production; the prepared manganese lithium phosphate/carbon composite material has a primary particle average diameter of 40-500 nm; the synthetic manganese lithium phosphate/carbon composite material has good electrochemical property when taken as the anode material of the lithium battery, high specific capacity and nice circulating performance at the conditions of room temperature and large current density; and the specific discharge capacity with 0.1 C multiplying power is more than 130 mAh/g.
Description
Technical field
The invention belongs to the energy and material technical field, particularly a kind of method for preparing the manganese phosphate lithium/carbon composite material with manganese phosphate.
Background technology
Since reported first olivine-type LiFePO 4 in 1997 has reversible removal lithium embedded function, phosphate of olivine type class intercalation materials of li ions LiMPO
4(M=Mn, Fe, Co, Ni) received extensive concern because of its higher structural stability as anode material for lithium-ion batteries.LiMnPO wherein
4With respect to Li/Li
+Electrode potential be 4.1V, be positioned at the stable electrochemical window of existing electrolyte system, and this material has the theoretical specific capacity up to 171mAh/g, have high energy density.In addition, its raw materials used aboundresources, low price, environmental friendliness, LiMnPO
4The Stability Analysis of Structures of material own has potential high security, is considered to a kind of promising anode material for lithium-ion batteries.
But LiMnPO
4Also has inevitable shortcoming during as positive electrode.At first, LiMnPO
4The room temperature electronic conductivity low, this can be through at LiMnPO
4Particle surface coated with conductive material (like carbon) or ion doping improve; Secondly, Li
+At LiMnPO
4In diffusion admittance be one dimension, thereby diffusion velocity is slow, makes that the high rate during charging-discharging of material is poor, the utilance of active material is on the low side, this can improve through reducing the material granule degree.
At present synthetic LiMnPO
4Method mainly contain high-temperature solid phase reaction method, liquid-phase coprecipitation, sol-gal process, hydro thermal method, hydrolytic precipitation method and mechanical ball milling method.Wherein the use of high-temperature solid phase reaction method is the most extensive, also the most suitable suitability for industrialized production.The emerging research group of domestic Wang Zhi has carried out research (Central South University's journal (natural science edition), 2005,36 (6): 960-964 for many years to this; Acta PhySico-Chimica Sinica, 2004,20 (10): 1249-1252; The China YouSe Acta Metallurgica Sinica, 2008,18 (4): 660-665), its typical building-up process is formed LiMnPO for pressing
4Stoichiometric proportion take by weighing Li
2CO
3, MnCO
3, NH
4H
2PO
4, and with an amount of carbon black (the Theoretical Mass ratio content of carbon in product is 10%) ball mill mixing, then at N
2Carry out the ball milling second time again behind the following 300 ℃ of pre-burning 3h of atmosphere, at N
2Carry out sintering in uniform temperature under the atmosphere and obtain product.These are synthetic all to use lithium salts, manganese salt and phosphate to be raw material, through pre-burning, add carbon reduction or hydrogen reducing roasting, operates more loaded down with trivial detailsly, has the purity problem of lower of sintetics.People (Journal of Alloys andCompounds 464 (2008) 259-264) such as Natalia N.Bramnik are then with NH
4MnPO
4H
2O and LiOHH
2O or Li
2CO
3By the stoichiometric proportion ball mill mixing, be pressed into bead then and burn 2 hours acquisition end products at 400 ℃.This method has only been used two kinds of raw materials, thereby can obtain product at lower temperature with in the short period, but NH
4MnPO
4H
2The preparation process more complicated of O, purity are restive.And patent CN 101320809A has improved the uniformity that lithium source, water-insoluble manganese source, phosphorus source and carbon source material mix through ball milling and spray drying.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the manganese phosphate lithium/carbon composite material with manganese phosphate.
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that this method step is following with manganese phosphate:
(1) with bivalent manganese source and phosphorus source solution according to mol ratio Mn: P=(1～3): 1 mix after; Adding excessive oxidant makes bivalent manganese be oxidized to manganic; And the pH value of regulator solution is 1～5.9; Stirring reaction 0.5～24 hour or 80～200 ℃ of hydro-thermal reactions of warp 2～72 hours after filtration, washing and drying, obtain active manganese phosphate (MnPO
4), said manganese phosphate has or does not have the crystallization water;
(2) according to mol ratio Li: Mn=(0.9～1.2): 1 takes by weighing the manganese phosphate of lithium source and step (1) gained, mixes, and adds carbon source; The carbon source addition is 5～50% of active manganese phosphate and a lithium source gross mass, and above-mentioned substance ball milling in liquid medium was carried out spray drying after 3～20 hours; Dried powder is heat-treated under protective atmosphere, is warming up to 300～850 ℃, calcines 2～12 hours; In the heat treated process; Manganic is reduced into bivalent manganese, and natural cooling obtains the manganese phosphate lithium/carbon composite material then.
Another technical scheme is that said carbon source adds in step (1), and bivalent manganese source is mixed with phosphorus source solution; After adding the pH value of excessive oxidant and regulator solution, add carbon source, make the concentration of carbon source be higher than 0.4mol/L and fully dissolving; Carry out stirring reaction or hydro-thermal reaction then; Through filtering, wash and drying, obtain manganese phosphate/carbon composite, in step (2), no longer add carbon source; The back spray drying is mixed in manganese phosphate/carbon composite and lithium source in liquid medium, dried powder is heat-treated under protective atmosphere.
Said bivalent manganese source is a kind of in manganese sulfate, manganese nitrate, manganese chloride or the manganese acetate.
Said phosphorus source is a kind of in sodium phosphate, potassium phosphate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or the ammonium dihydrogen phosphate.
Said lithium source is a kind of in lithium hydroxide, lithium carbonate, lithium oxalate or the lithium acetate.
Said carbon source is a kind of in glucose, fructose, sucrose, lactose, Super P, starch, PAN, PVC, PVB, PVA or the phenolic resins.
Said oxidant is nitric acid or hydrogen peroxide solution.
Said pH value is regulated with salpeter solution.
Said liquid medium is a kind of in deionized water, ethanol, the deionized water-ethanolic solution.
Said protective atmosphere is a kind of in the nitrogen, argon gas, hydrogen-nitrogen mixed gas, hydrogen-argon-mixed, and wherein, the volume content of hydrogen is 2～10% in hydrogen-nitrogen mixed gas, and the volume content of hydrogen is 2～10% in the hydrogen-argon-mixed.
Beneficial effect of the present invention is:
That the method for preparing lithium ion battery anode material manganese lithium phosphate/carbon composite of the present invention has is with low cost, synthesis technique simple, be fit to the characteristics of suitability for industrialized production; Through and control product granularity compound with material with carbon element; The equal lithium manganese phosphate positive electrode preferably of chemical property when obtaining room temperature with big electric current, its advantage is:
(1) adopt simple solution deposit to synthesize and have highly active manganese phosphate, and can finally control the particle diameter of lithium manganese phosphate through the particle diameter of control manganese phosphate, the manganese phosphate lithium/carbon composite material primary particle average grain diameter of gained is 40～500nm;
(2) adopt two kinds of compounds to prepare lithium manganese phosphate, effectively reduce the material diffusion in the solid phase reaction process, thereby help forming the higher lithium manganese phosphate of purity as reactant;
(3) adopt ball mill mixing and spray-dired method, with presoma rapid draing and be controlled to uniform spherical, the flowability of material when tap density that helps keeping the uniform admixture of raw material, improve material and preparation slurry;
(4) synthetic manganese phosphate lithium/carbon composite material has good electrochemical as anode material for lithium-ion batteries, under room temperature and high current density condition, has height ratio capacity and excellent cycle performance, and 0.1C multiplying power discharging specific capacity is more than 130mAh/g.
Embodiment
Below in conjunction with embodiment the present invention is described further:
Embodiment 1
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: the manganese nitrate of 0.4mol/L and 0.2mol/L sodium radio-phosphate,P-32 solution equal-volume are mixed (mol ratio Mn: P=2: 1), stir, the salpeter solution adjusting pH that uses 1mol/L is that 4 (nitric acid is also made oxidant; Make bivalent manganese be oxidized to manganic, the amount of regulating the used nitric acid of pH value can guarantee that oxidant is excessive), stirring reaction is after 3 hours; Suction filtration; Use deionized water and washing with alcohol successively, drying obtains active manganese phosphate (MnPO
4), said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium carbonate according to mol ratio Li: Mn=1.05, mix, and add sucrose, the sucrose addition is 15% of active manganese phosphate and a lithium carbonate gross mass; Above-mentioned substance is carried out ball milling, with ethanol as decentralized medium, with the rotating speed ball milling of 350rpm after 10 hours; Carry out spray drying, dried powder is heat-treated in high pure nitrogen stream, is warming up to 400 ℃ with the heating rate of 5 ℃/min; Calcined 6 hours, in the heat treated process, manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and the distribution of its grain diameter is 100～500nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 145mAh/g.
Embodiment 2
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: the preparation of manganese phosphate is with embodiment 1;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium carbonate according to mol ratio Li: Mn=1.1, mix, and add phenolic resins-ethanolic solution; The amount of phenolic resins is 20% of active manganese phosphate and a lithium carbonate gross mass in the phenolic resins-ethanolic solution that adds, and above-mentioned substance is carried out ball milling, with ethanol as decentralized medium; After 10 hours, carry out spray drying with the rotating speed ball milling of 350rpm, dried powder is heat-treated in high pure nitrogen stream; Heating rate with 5 ℃/min is warming up to 600 ℃, calcines 12 hours, in the heat treated process; Manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and its primary particle average grain diameter is 100nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 135mAh/g.
Embodiment 3
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: manganese chloride and the 0.2mol/L potassium phosphate solution equal-volume of 0.3mol/L are mixed (mol ratio Mn: P=1.5: 1), stir, add hydrogen peroxide solution by stoichiometric proportion; Make bivalent manganese be oxidized to manganic, and to use the salpeter solution of 1mol/L to regulate pH be 2, stirring reaction is after 5 hours; Suction filtration; Use deionized water and washing with alcohol successively, drying obtains active manganese phosphate (MnPO
4), said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium carbonate according to mol ratio Li: Mn=1.05, mix, and add glucose, the glucose addition is 40% of active manganese phosphate and a lithium carbonate gross mass; Above-mentioned substance is carried out ball milling, with deionized water as decentralized medium, with the rotating speed ball milling of 350rpm after 10 hours; Carry out spray drying, dried powder is heat-treated in high pure nitrogen stream, is warming up to 600 ℃ with the heating rate of 5 ℃/min; Calcined 10 hours, in the heat treated process, manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and its primary particle average grain diameter is 120nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 147mAh/g.
Embodiment 4
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: according to mol ratio Mn: P=1.8: 1, in the sodium radio-phosphate,P-32 solution of 0.2mol/L, dropwise add the manganese sulfate solution of 3mol/L, obtain post precipitation; The hydrogen peroxide solution that adds 2 times of stoichiometric proportions makes bivalent manganese be oxidized to manganic, regulates pH to 5.9 with the salpeter solution of 1mol/L, and the gained suspension-turbid liquid is poured in the water heating kettle; Reaction is 72 hours under 150 ℃ temperature; Naturally cool to room temperature, suction filtration is used deionized water and washing with alcohol successively; Drying obtains active manganese phosphate (MnPO
4), said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium hydroxide according to mol ratio Li: Mn=1.0, mix, and add phenolic resins-ethanolic solution; The amount of phenolic resins is 20% of active manganese phosphate and a lithium hydroxide gross mass in the phenolic resins-ethanolic solution that adds, and above-mentioned substance is carried out ball milling, with deionized water as decentralized medium; After 10 hours, carry out spray drying with the rotating speed ball milling of 350rpm, dried powder is heat-treated in high pure nitrogen stream; Heating rate with 5 ℃/min is warming up to 700 ℃, calcines 5 hours, in the heat treated process; Manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and its primary particle average particle size distribution is 40～500nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 140mAh/g.
Embodiment 5
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: under the condition of magnetic agitation, according to mol ratio Mn: P=1.3: 1, in the sodium radio-phosphate,P-32 solution of 0.2mol/L, dropwise add the manganese nitrate solution of 4.3mol/L; Obtain post precipitation, (nitric acid is also made oxidant, makes bivalent manganese be oxidized to manganic to regulate pH to 5.9 with the salpeter solution of 1mol/L; The amount of regulating the used nitric acid of pH value can guarantee that oxidant is excessive), the gained suspension-turbid liquid is poured in the water heating kettle, reaction is 72 hours under 150 ℃ temperature; Naturally cool to room temperature, suction filtration is used deionized water and washing with alcohol successively; Drying obtains active manganese phosphate (MnPO
4), said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium oxalate according to mol ratio Li: Mn=1.05, mix, and add glucose, the glucose addition is 25% of active manganese phosphate and a lithium oxalate gross mass; Above-mentioned substance is carried out ball milling, with deionized water as decentralized medium, with the rotating speed ball milling of 350rpm after 10 hours; Carry out spray drying, dried powder is heat-treated in high pure nitrogen stream, is warming up to 800 ℃ with the heating rate of 5 ℃/min; Calcined 5 hours, in the heat treated process, manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and its primary particle average grain diameter is 200nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 132mAh/g.
Embodiment 6
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate: under the condition of magnetic agitation, according to mol ratio Mn: P=2: 1, in the sodium radio-phosphate,P-32 solution of 0.2mol/L, dropwise add the manganese nitrate solution of 4.3mol/L; Obtain post precipitation, (nitric acid is also made oxidant, makes bivalent manganese be oxidized to manganic to regulate pH to 3 with the salpeter solution of 1mol/L; The amount of regulating the used nitric acid of pH value can guarantee that oxidant is excessive), the gained suspension-turbid liquid is poured in the water heating kettle, reaction is 72 hours under 150 ℃ temperature; Naturally cool to room temperature, suction filtration is used deionized water and washing with alcohol successively; Drying obtains active manganese phosphate (MnPO
4), said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate and lithium acetate according to mol ratio Li: Mn=1.2, mix, and add glucose; The glucose addition is 20% of active manganese phosphate and a lithium acetate gross mass, and above-mentioned substance is carried out ball milling, with deionized water as decentralized medium; After 10 hours, carry out spray drying with the rotating speed ball milling of 350rpm, dried powder is heat-treated in high pure nitrogen stream; Heating rate with 5 ℃/min is warming up to 700 ℃, calcines 2 hours, in the heat treated process; Manganic is reduced into bivalent manganese; Natural cooling obtains the manganese phosphate lithium/carbon composite material then, and its primary particle average grain diameter is 100～500nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 145mAh/g.
Embodiment 7
A kind ofly prepare the method for manganese phosphate lithium/carbon composite material with manganese phosphate, this method step is following:
(1) preparation manganese phosphate/carbon composite: under the condition of magnetic agitation, according to mol ratio Mn: P=2.5: 1, in the sodium radio-phosphate,P-32 solution of 0.2mol/L, dropwise add the manganese nitrate solution of 4.3mol/L; Obtain post precipitation, (nitric acid is also made oxidant, makes bivalent manganese be oxidized to manganic to regulate pH to 4 with the salpeter solution of 1mol/L; The amount of regulating the used nitric acid of pH value can guarantee that oxidant is excessive), in the gained suspension-turbid liquid, be higher than 0.4mol/L and fully dissolving by the concentration that adds glucose to glucose, pour in the water heating kettle then; Reaction is 48 hours under 180 ℃ temperature; Naturally cool to room temperature, suction filtration is used deionized water and washing with alcohol successively; Drying obtains active manganese phosphate (MnPO
4)/carbon composite, said manganese phosphate has the crystallization water;
(2) preparation manganese phosphate lithium/carbon composite material: take by weighing active manganese phosphate/carbon composite and lithium acetate according to mol ratio Li: Mn=1.05, mix, above-mentioned substance is carried out ball milling; As decentralized medium, after 10 hours, carry out spray drying with deionized water with the rotating speed ball milling of 350rpm; Dried powder is heat-treated (hydrogen-argon-mixed middle hydrogen volume content is 5%) in hydrogen-argon-mixed stream, be warming up to 700 ℃ with the heating rate of 5 ℃/min, calcines 2 hours; In the heat treated process, manganic is reduced into bivalent manganese, then natural cooling; Obtain the manganese phosphate lithium/carbon composite material, its primary particle average grain diameter is 50nm.
The manganese phosphate lithium/carbon composite material of present embodiment preparation is an anode material for lithium-ion batteries, is negative pole assembling button cell with the lithium sheet, and the specific discharge capacity of this manganese phosphate lithium/carbon composite material 0.1C multiplying power is 147mAh/g.
Material of the present invention adopts button cell test chemical property, scanning electron microscopic observation sample particle degree and pattern, powder x-ray diffraction appearance to measure crystalline phase respectively, and test result shows that material has olivine LiMnPO preferably
4Structure, made manganese phosphate lithium/carbon composite material primary particle average grain diameter is 40～500nm, 0.1C multiplying power discharging specific capacity is more than 130mAh/g.
Claims (10)
1. one kind prepares the method for manganese phosphate lithium/carbon composite material with manganese phosphate, it is characterized in that this method step is following:
(1) with bivalent manganese source and phosphorus source solution according to mol ratio Mn: P=(1～3): 1 mix after; Adding excessive oxidant makes bivalent manganese be oxidized to manganic; And the pH value of regulator solution is 1～5.9; Stirring reaction 0.5～24 hour or 80～200 ℃ of hydro-thermal reactions of warp 2～72 hours after filtration, washing and drying, obtain active manganese phosphate (MnPO
4), said manganese phosphate has or does not have the crystallization water;
(2) according to mol ratio Li: Mn=(0.9～1.2): 1 takes by weighing the manganese phosphate of lithium source and step (1) gained, mixes, and adds carbon source; The carbon source addition is 5～50% of active manganese phosphate and a lithium source gross mass, and above-mentioned substance ball milling in liquid medium was carried out spray drying after 3～20 hours; Dried powder is heat-treated under protective atmosphere, is warming up to 300～850 ℃, calcines 2～12 hours; In the heat treated process; Manganic is reduced into bivalent manganese, and natural cooling obtains the manganese phosphate lithium/carbon composite material then.
2. one kind prepares the method for manganese phosphate lithium/carbon composite material with manganese phosphate, it is characterized in that this method step is following:
(1) with bivalent manganese source and phosphorus source solution according to mol ratio Mn: P=(1～3): 1 mix after; Add excessive oxidant and make bivalent manganese be oxidized to manganic, and after the pH value of regulator solution is 1～5.9, add carbon source; Make the concentration of carbon source be higher than 0.4mol/L and fully dissolving; Carried out stirring reaction then 0.5～24 hour or through 80～200 ℃ of hydro-thermal reactions 2～72 hours, through filter, washing and dry, obtain manganese phosphate/carbon composite;
(2) according to mol ratio Li: Mn=(0.9～1.2): 1 takes by weighing the manganese phosphate/carbon composite of lithium source and step (1) gained, and manganese phosphate/carbon composite and lithium source mixing and ball milling in liquid medium was carried out spray drying after 3～20 hours; Dried powder is heat-treated under protective atmosphere, is warming up to 300～850 ℃, calcines 2～12 hours; In the heat treated process; Manganic is reduced into bivalent manganese, and natural cooling obtains the manganese phosphate lithium/carbon composite material then.
3. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said bivalent manganese source is a kind of in manganese sulfate, manganese nitrate, manganese chloride or the manganese acetate with manganese phosphate.
4. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said phosphorus source is a kind of in sodium phosphate, potassium phosphate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate or the ammonium dihydrogen phosphate with manganese phosphate.
5. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said lithium source is a kind of in lithium hydroxide, lithium carbonate, lithium oxalate or the lithium acetate with manganese phosphate.
6. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said carbon source is a kind of in glucose, fructose, sucrose, lactose, Super P, starch, PAN, PVC, PVB, PVA or the phenolic resins with manganese phosphate.
7. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said oxidant is nitric acid or hydrogen peroxide solution with manganese phosphate.
8. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said pH value regulates with salpeter solution with manganese phosphate.
9. according to claim 1 and 2ly a kind ofly prepare the method for manganese phosphate lithium/carbon composite material, it is characterized in that said liquid medium is a kind of in deionized water, ethanol, the deionized water-ethanolic solution with manganese phosphate.
10. a kind of method for preparing the manganese phosphate lithium/carbon composite material with manganese phosphate according to claim 1 and 2; It is characterized in that said protective atmosphere is a kind of in the nitrogen, argon gas, hydrogen-nitrogen mixed gas, hydrogen-argon-mixed; Wherein, The volume content of hydrogen is 2～10% in hydrogen-nitrogen mixed gas, and the volume content of hydrogen-argon-mixed middle hydrogen is 2～10%.
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| CN103794789B (en) * | 2014-03-12 | 2016-01-20 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery ferrous phosphate manganese lithium anode material and preparation method thereof |
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Application publication date: 20100317 Assignee: Jiangsu annals of New Energy Materials Technology Co., Ltd. Assignor: Tsinghua University Contract record no.: 2017990000152 Denomination of invention: Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate Granted publication date: 20120208 License type: Common License Record date: 20170426 |