CN103199239A - Ferrum-base lithium-enriched anode material and rheological phase preparation method - Google Patents
Ferrum-base lithium-enriched anode material and rheological phase preparation method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 238000000518 rheometry Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 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 2
- 238000001035 drying Methods 0.000 abstract description 9
- 238000007789 sealing Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910002983 Li2MnO3 Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 90
- 235000006408 oxalic acid Nutrition 0.000 description 30
- 238000005303 weighing Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 239000000376 reactant Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 235000015110 jellies Nutrition 0.000 description 8
- 239000008274 jelly Substances 0.000 description 8
- 229940071125 manganese acetate Drugs 0.000 description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a Ferrum-base lithium-enriched anode material and a rheological phase preparation method, and belongs to the technical field of Ferrum-base lithium-enriched anode materials, namely novel materials (1-x)Li2MnO3*xLiFe(1-y)CoyO2 and (1-x)Li2Mn1-0.5zMo0.5z03*xLiFe(1-z)Mo0.5zO2, wherein x is more than 0 and less than 1, y is more than 0 and less than 0.5, and z is more than 0 and less than 0.03. The rheological phase preparation method comprises the following steps of: mixing low-melting-point salt of lithium, Ferrum, manganese and cobalt or easily decomposable salt of molybdenum according to a proportion, and heating for fusion; adding neutral substances containing hydroxy or carboxyl or an aqueous solution of the neutral substances, stirring under a sealing condition, making metal salt surfaces be fully alkylated, and obtaining a rheological phase under an open system; and drying, preheating under the air at the temperature of 300-400 DEG C for 8 hours, heating to 500-650 DEG C, calcining for 10 hours, and naturally cooling the product. The technology is simple and is easy to operate; the cost is low; and the Ferrum-base lithium-enriched anode material is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of easy manufacture lithium ion anode material (1-x) Li
2MnO
3XLiFeO
2The method of rheology phase, and carried out the modification of doping Co and Mo on this basis, belong to iron-based lithium-rich anode material technical field.
Background technology
Since the cheap environmental friendliness of Fe, and reserves are abundant, so select for use iron containing compounds to replace LiCoO as positive electrode
2Research paid close attention to by the people gradually.At present, business-like LiFePO
4Be a kind of outstanding 3V positive electrode, but more and more researchers attempt seeking the 4V positive electrode of a Fe base.Because Li
2MnO
3It is higher to contain the lithium amount, and a series of solid solution positive electrodes that it is drawn are subjected to great concern, Fe on the other hand
3+/4+Oxidation-reduction pair is discharging and recharging about 4V the LiNiO that can mix at Fe
2LiCoO with the Fe doping
2In be observed, but at the active phase LiFeO of non-electrochemical
2In be not confirmed, so rich lithium material (1-x) Li of positive electrode iron-based
2MnO
3XLiFeO
2Be devised.This material has higher specific capacity, and material price is cheap.But (1-x) Li
2MnO
3XLiFeO
2Positive electrode must accomplish＜and the particle size of 100nm just has chemical property, and present synthetic method mainly is low temperature co-precipitation-hydro-thermal-high-temperature calcination three-step approach, and building-up process is comparatively loaded down with trivial details, and cycle performance is not good.Therefore, a kind of can synthesizing of active demand can access the synthetic method that is lower than the 100nm particle size, can improve cyclical stability simultaneously.
Rheology phase method is a kind of softening method, is the chemical reaction that has rheology to participate in mutually in reaction system, is that a kind of software that rheology is combined with synthetic method is learned green synthesis method.Specifically be just multiple solid-phase reactant after preliminary the mixing, add proper amount of solvent, the rheology system of not stratified, the homogeneous that forms that solid mixture and solvent fully contact places this system under the appropriate reaction conditions to obtain presoma.This synthetic method is extensively quoted in the synthesis of nano particle, and the surface area of solid particle can effectively be utilized, in the reaction heat exchange good, the local overheating phenomenon can not appear, temperature is easy to regulate.
Summary of the invention
The invention provides a kind of novel preparation lithium ion anode material (1-x) Li
2MnO
3XLiFeO
2Rheology phase method, 0＜x＜1 wherein, this method can obtain the particle less than the 100nm size, the good cycle of material, and technology is simple, the easy row, with low cost of operation, environmental friendliness is suitable for large-scale industrial production.We have also carried out doping vario-property on this basis, the rich lithium composite material of the synthetic ferrimanganic that makes new advances, (1-x) Li
2MnO
3XLiFe
(1-y)Co
yO
2(0＜x＜1,0＜y＜0.5) and (1-x) Li
2Mn
1-0.5zMo
0.5zO
3XLiFe
(1-z)Mo
0.5zO
2(0＜x＜1,0＜z＜0.03), these materials still keep the sized particles less than 100nm, but have improved cycle performance effectively.
The technical scheme that solution the technology of the present invention problem adopts is as follows.
The covert legal system of a kind of simple stream is equipped with iron-based lithium-rich anode material (1-x) Li
2MnO
3XLiFeO
2Method, wherein 0＜x＜1 is characterized in that, may further comprise the steps:
(1) the low melting point salt with lithium, iron, manganese mixes in proportion, stirs under condition of water bath heating, forms molten state;
(2) add in the mixture and contain the neutral organic substance of hydroxyl or carboxyl or the aqueous solution of neutral organic substance, under air-proof condition, continue to stir a period of time, make the fully alkylation of slaine surface, under the system of opening wide, obtain the rheology phase afterwards;
(3) above-mentioned rheology is dried down at 120 ℃, grinding obtains powder, move in the high temperature furnace, under air atmosphere in 300 ℃～400 ℃ preheatings 8 hours, make salt decompose, be warmed up to 500～650 ℃ of calcinings of high temperature 10 hours then, naturally cool to room temperature then, namely obtain anode material for lithium-ion batteries (1-x) Li
2MnO
3XLiFeO
2
The rich lithium composite material of the ferrimanganic that a kind of Co or Mo mix is characterized in that its chemical formula is as follows: (1-x) Li
2MnO
3XLiFe
(1-y)Co
yO
2(0＜x＜1,0＜y＜0.5) and (1-x) Li
2Mn
1-
0.5zMo
0.5zO
3XLiFe
(1-
Z)Mo
0.5zO
2(0＜x＜1,0＜z＜0.03).
The preparation method of the rich lithium composite material of the ferrimanganic that above-mentioned Co or Mo mix may further comprise the steps:
(1) the easy decomposition salt with low melting point salt such as the acetate of lithium, iron, manganese, cobalt or nitrate or molybdenum mixes in proportion, stirs under condition of water bath heating, forms molten state;
(2) add in the mixture and contain the neutral organic substance of hydroxyl or carboxyl or the aqueous solution of neutral organic substance, under air-proof condition, continue to stir a period of time, make the fully alkylation of slaine surface, under the system of opening wide, obtain the rheology phase afterwards;
(3) above-mentioned rheology is dried down at 120 ℃, grinding obtains powder, move in the high temperature furnace, under air atmosphere in 300 ℃～400 ℃ preheatings 8 hours, make salt decompose, be warmed up to 500～650 ℃ of calcinings of high temperature 10 hours then, naturally cool to room temperature then, namely obtain rich lithium material (1-x) Li of iron-based
2MnO
3XLiFe
(1-y)Co
yO
2(0＜x＜1,0＜y＜0.5) and (1-x) Li
2Mn
1-0.5zMo
0.5zO
3XLiFe
(1-z)Mo
0.5zO
2(0＜x＜1,0＜z＜0.03).
The lithium salts excessive 5% of preferred steps (1).
About using rich lithium material average grain diameter of this ferrimanganic that the method obtains as 50nm, even particle distribution has following advantage than additive method:
(1) with (1-x) Li
2MnO
3XLiFeO
2Co-precipitation-hydro-thermal-high-end calcining synthetic method compare, simplified technological process, and reduced synthesis temperature.
(2) compare with conventional solid-state method, be easy to the even mixing of realization response thing, compare than other wet chemical method, technological process is simple, and cost is lower, is easy to industrialized realization.
(3) compare other rheology phase method, allow metallic salt form the fused salt attitude early stage can be so that metal ion be tentatively mixed, through closed processes a period of time, the abundant alkylation of the surface of solids that can reactant, allow solvent evaporates under the system opening wide afterwards, just can obtain the rheology phase system rapidly, accelerated reaction is carried out.
(4) the adding composite material that Co and Mo synthesized can obviously improve the cycle performance of material, increases circulation volume.
Description of drawings
The XRD figure of the positive electrode that Fig. 1 embodiment 1-3 is prepared, A is that embodiment 1 is prepared, and B is that embodiment 2 is prepared, and C is that embodiment 3 is prepared;
The SEM figure of the positive electrode that Fig. 2 embodiment 1-3 is prepared, A is that embodiment 1 is prepared, and B is that embodiment 2 is prepared, and C is that embodiment 3 is prepared;
The cycle performance comparison diagram of the positive electrode that Fig. 3 embodiment 1-3 is prepared;
The XRD figure of the positive electrode that Fig. 4 embodiment 4-5 is prepared, A is that embodiment 4 is prepared, B is that embodiment 5 is prepared;
The SEM figure of the positive electrode that Fig. 5 embodiment 4-5 is prepared, A is that embodiment 4 is prepared, B is that embodiment 5 is prepared;
The XPS collection of illustrative plates of the positive electrode that Fig. 6 embodiment 5 is prepared, A is the Co element, and B is the Fe element, and C is the Mn element;
The cycle performance comparison diagram of the positive electrode that Fig. 7 embodiment 4-5 is prepared;
The XRD figure of the positive electrode that Fig. 8 embodiment 6-8 is prepared, A is that embodiment 6 is prepared, and B is that embodiment 7 is prepared, and C is that embodiment 8 is prepared;
The SEM figure of the positive electrode that Fig. 9 embodiment 6-8 is prepared, A is that embodiment 6 is prepared, and B is that embodiment 7 is prepared, and C is that embodiment 8 is prepared;
The XPS collection of illustrative plates of the positive electrode that Figure 10 embodiment 7 is prepared, A is the Mo element, and B is the Fe element, and C is the Mn element;
The cycle performance comparison diagram of the positive electrode that Figure 11 embodiment 6-8 is prepared.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but the present invention is not limited to following examples.
Embodiment 1
With synthetic 0.9Li
2MnO
30.1LiFeO
2Be example, according to taking by weighing lithium acetate 15.2647g(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 2.0200g, manganese acetate 16.5436g.Put into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode is 1:2, the water-soluble solution that adds 30ml, splash into again about ammoniacal liquor adjusting PH to 7 and make oxalic acid solution, after the sealing, stirred 2 hours down for 90 ℃ in water-bath, under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.9Li
2MnO
30.1LiFeO
2
With the positive electrode of gained according to 0.9Li
2MnO
30.1LiFeO
2: acetylene black: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 2
With synthetic 0.8Li
2MnO
30.2LiFeO
2Be example, take by weighing lithium nitrate 11.0182g(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 6.0600g, manganese acetate 14.7054g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode is 1:2, the water-soluble solution that adds 30ml, splash into again about ammoniacal liquor adjusting PH to 7 and make oxalic acid solution, after the sealing, stirred 2 hours down for 90 ℃ in water-bath, under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.8Li
2MnO
30.2LiFeO
2
With the positive electrode of gained according to 0.8Li
2MnO
30.2LiFeO
2: acetylene black: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 3
With synthetic 0.7Li
2MnO
30.3LiFeO
2Be example, take by weighing lithium acetate 6.8398(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 6.0600g, manganese acetate 6.4460g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2MnO
30.3LiFeO
2
With the positive electrode of gained according to 0.7Li
2MnO
30.3LiFeO
2: acetylene black: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 4
With synthetic 0.7Li
2MnO
30.3LiFe
0.67Co
0.33O
2Be example, take by weighing lithium acetate 6.8398(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 4.0400g, manganese acetate 6.4460g, cobalt nitrate 1.4552g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Stirred 2 hours down for 90 ℃ in water-bath, under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2MnO
30.3LiFe
0.67Co
0.33O
2
With the positive electrode of gained according to 0.7Li
2MnO
30.3LiFe
0.67Co
0.33O
2: acetylene black: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 5
With synthetic 0.7Li
2MnO
30.3LiFe
0.75Co
0.25O
2Be example, take by weighing lithium acetate 6.8398(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 4.545g, manganese acetate 6.4460g, cobalt nitrate 1.0914g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2MnO
30.3LiFeO
2
With the positive electrode of gained according to 0.7Li
2MnO
30.3LiFeO
2: acetylene black: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 6
With synthetic 0.7Li
2Mn
0.995Mo
0.005O
30.3LiFe
0.995Mo
0.005O
2Be example, take by weighing lithium acetate 9.2759g(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 6.0600g, manganese acetate 8.67922g, ammonium molybdate 0.0899g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2Mn
0.995Mo
0.005O
30.3LiFe
0.995Mo
0.005O
2
With the positive electrode of gained according to positive electrode: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10 acetylene black:, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Embodiment 7
With synthetic 0.7Li
2Mn
0.99Mo
0.01O
30.3LiFe
0.99Mo
0.01O
2Be example, take by weighing lithium acetate 9.4342g(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 6.0600g, manganese acetate 8.7643g, ammonium molybdate 0.1829g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2Mn
0.995Mo
0.005O
30.3LiFe
0.995Mo
0.005O
2
With the positive electrode of gained according to positive electrode: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10 acetylene black:, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
With synthetic 0.7Li
2Mn
0.985Mo
0.015O
30.3LiFe
0.985Mo
0.015O
2Be example, take by weighing lithium acetate 9.5997g(excessive 5% according to Li, Fe, Mn molar ratio), ferric nitrate 6.0600g, manganese acetate 8.8535g, ammonium molybdate 0.2788g puts into reactor.Weighing oxalic acid, the mol ratio of oxalic acid and positive electrode are 1:2, add the water-soluble solution of 30ml, splash into about ammoniacal liquor adjusting PH to 7 again and make oxalic acid solution.Oxalic acid solution is also added in the reactor, after the sealing, stirred 2 hours.Under the system of opening wide, continue afterwards to stir, obtain the rheology phase, reactant is fully mixed.
After whole system becomes jelly, stop to stir.Reactant is placed 120 ℃ of oven dry 10h in the drying box.Product is pulverized last, and the programming rate with 1 ℃/min under high temperature furnace rises to 350 ℃, and insulation is 8 hours under air atmosphere, rises to 550 ℃ of calcining 10h afterwards.Obtain iron-based lithium-rich anode material 0.7Li
2Mn
0.995Mo
0.005O
30.3LiFe
0.995Mo
0.005O
2
With the positive electrode of gained according to positive electrode: PTFE(fluoro polyethylene)=the accurate weighing of mass ratio of 80::10:10 acetylene black:, mix and make electrode slice after compressing tablet is handled, with LiPF
6For electrolyte is assembled into button cell being full of in the glove box of argon gas atmosphere.
Claims (7)
1. the covert legal system of simple stream is equipped with iron-based lithium-rich anode material (1-x) Li
2MnO
3XLiFeO
2Method, wherein 0＜x＜1 is characterized in that, may further comprise the steps:
(1) the low melting point salt with lithium, iron, manganese mixes in proportion, stirs under condition of water bath heating, forms molten state;
(2) add in the mixture and contain the neutral organic substance of hydroxyl or carboxyl or the aqueous solution of neutral organic substance, under air-proof condition, continue to stir a period of time, make the fully alkylation of slaine surface, under the system of opening wide, obtain the rheology phase afterwards;
(3) above-mentioned rheology is dried down at 120 ℃, grinding obtains powder, move in the high temperature furnace, under air atmosphere in 300 ℃～400 ℃ preheatings 8 hours, make salt decompose, be warmed up to 500～650 ℃ of calcinings of high temperature 10 hours then, naturally cool to room temperature then, namely obtain anode material for lithium-ion batteries (1-x) Li
2MnO
3XLiFeO
2
2. according to the method for claim 1, it is characterized in that described low melting point salt is acetate or nitrate.
3. according to the method for claim 1, it is characterized in that the lithium salts excessive 5% of step (1).
4. the rich lithium composite material of ferrimanganic that mixes of a Co or Mo is characterized in that its chemical formula is as follows: (1-x) Li
2MnO
3XLiFe
(1-y)Co
yO
2(1-x) Li
2Mn
1-0.5zMo
0.5zO
3XLiFe
(1-z)Mo
0.5zO
2, 0＜x＜1,0＜y＜0.5,0＜z＜0.03.
5. the method for the rich lithium composite material of ferrimanganic of a kind of Co of preparation claim 4 or Mo doping is characterized in that, may further comprise the steps:
(1) the low melting point salt with lithium, iron, manganese, cobalt mixes in proportion, and perhaps just the easy decomposition salt of the low melting point salt of lithium, iron, manganese and molybdenum mixes in proportion, stirs under condition of water bath heating, forms molten state;
(2) add in the mixture and contain the neutral organic substance of hydroxyl or carboxyl or the aqueous solution of neutral organic substance, under air-proof condition, continue to stir a period of time, make the fully alkylation of slaine surface, under the system of opening wide, obtain the rheology phase afterwards;
(3) above-mentioned rheology is dried down at 120 ℃, grinding obtains powder, move in the high temperature furnace, under air atmosphere in 300 ℃～400 ℃ preheatings 8 hours, make salt decompose, be warmed up to 500～650 ℃ of calcinings of high temperature 10 hours then, naturally cool to room temperature then, namely obtain rich lithium material (1-x) Li of iron-based
2MnO
3XLiFe
(1-y)Co
yO
2(1-x) Li
2Mn
1-0.5zMo
0.5zO
3XLiFe
(1-z)Mo
0.5zO
2
6. according to the method for claim 5, it is characterized in that described low melting point salt is acetate or nitrate.
7. according to the method for claim 5, it is characterized in that the lithium salts excessive 5% of step (1).
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| CN107293742A (en) * | 2017-07-25 | 2017-10-24 | 黄冈林立新能源科技有限公司 | A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology |
| CN111017999A (en) * | 2019-12-13 | 2020-04-17 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
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| CN107293742A (en) * | 2017-07-25 | 2017-10-24 | 黄冈林立新能源科技有限公司 | A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology |
| CN111017999A (en) * | 2019-12-13 | 2020-04-17 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
| CN111017999B (en) * | 2019-12-13 | 2021-11-30 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
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