CN1461064A - Method for preparing lithium manganese oxide by using low-heat solid phase reaction - Google Patents
Method for preparing lithium manganese oxide by using low-heat solid phase reaction Download PDFInfo
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- CN1461064A CN1461064A CN03131933A CN03131933A CN1461064A CN 1461064 A CN1461064 A CN 1461064A CN 03131933 A CN03131933 A CN 03131933A CN 03131933 A CN03131933 A CN 03131933A CN 1461064 A CN1461064 A CN 1461064A
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- acid
- lithium
- manganese oxide
- manganese
- solid phase
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title claims abstract description 16
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims abstract description 16
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001413 amino acids Chemical class 0.000 claims abstract description 5
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000011651 chromium Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- 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
- 229910015645 LiMn Inorganic materials 0.000 claims description 10
- 229910014689 LiMnO Inorganic materials 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 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 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- 235000013922 glutamic acid Nutrition 0.000 claims description 5
- 239000004220 glutamic acid Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 235000001014 amino acid Nutrition 0.000 claims description 4
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims description 4
- 206010037660 Pyrexia Diseases 0.000 claims description 3
- 235000011087 fumaric acid Nutrition 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000185 sucrose group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 4
- 229910006264 Li1+xMn2O4 Inorganic materials 0.000 abstract 1
- 229910002993 LiMnO2 Inorganic materials 0.000 abstract 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 150000002696 manganese Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- -1 manganese metals Chemical class 0.000 description 1
- 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 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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 method for preparing lithium-manganese oxide by using low-beat solid phase reaction includes the following steps: according to stoichiometric ratio mixing lithium acetate, manganese acetate and solid phase organic acid or alcohol or sugar or amino acid; grinding at room temp., drying the obtained mixture at 75-85 deg.C and calcining at 350-850 deg.c for 12-18 hr. so as to obtain the invented final product Li1+xMn2O4 or Li1+xMnO2, in which x=-0.1-+0.2. According to different stoichiometric ratio the spinelle type LiMn2O4 or laminate LiMnO2 can be obtained.
Description
One, technical field
The present invention relates to the method that lithium, manganese salt prepare lithium manganese oxide.
Two, background technology
In recent years, have that volume is little, the lithium ion battery of light weight, specific energy height, memory-less effect or the like advantage become the focus of whole world research, and the most important just link of the selection of anode material for lithium-ion batteries.With respect to LiCoO
2And LiNiO
2, the LiMn of spinel-type
2O
4LiMnO with stratiform
2Advantages such as it is abundant to have the manganese metals resources, and cheap, the preparation method is simple, and environmental pollution is little, so they are considered to the most promising positive electrode of lithium rechargeable battery of new generation.
The tradition solid reaction process directly adopts lithium salts and manganese salt mixed calcining to prepare lithium manganese compound, but this method products therefrom particle is big and inhomogeneous, the difficult control of stoichiometric proportion, and the reaction temperature height, the time is long, cost is high, and easily causes the loss of lithium.
Three, summary of the invention
The purpose of this invention is to provide a kind of LiMn that makes lithium salts and manganese salt solid phase reaction prepare spinel-type at a lower temperature
2O
4Or the LiMnO of stratiform
2Method.Another object of the present invention provides the method that the above-mentioned lithium manganese oxide of Cr or Y metal ion is mixed in preparation.
Technical scheme of the present invention is as follows:
A kind of low fever solid phase reaction prepares the method for lithium manganese oxide, and it is made up of the following step:
Step 1, the organic acid of lithium acetate, manganese acetate and solid phase or alcohol or sugar or amino acid are mixed by stoichiometric proportion, at room temperature grind, so that mixture mixes, the ratio (as follows) of their amount of substances is: (lithium+manganese): organic substance=1: 0.4～1: 2, preferably (lithium+manganese): organic substance=1: 1～1.2
Step 2, mixture that step 1 is obtained after 75～85 ℃ of dryings, 350～850 ℃ down calcining promptly obtained end product Li in 12～18 hours
1+xMn
2O
4Or Li
1+xMnO
2, X=-0.1～0.2 wherein.According to the stoichiometric proportion difference, can obtain the LiMn of spinel-type
2O
4Or the LiMnO of stratiform
2, the LiMn of preparation spinel-type
2O
4Preferred calcining heat is 550 ℃-600 ℃, the LiMnO of preparation stratiform
2Preferred calcining heat is 400 ℃-450 ℃.
The above-mentioned method for preparing lithium manganese oxide is at preparation LiMn
2O
4Step 1 in, can in lithium acetate and manganese acetate, add the chromium carbonate or three yittrium oxide of stoichiometric proportion, the end product that obtains is Li
1+xCr
yMn
2-yO
4Or Li
1+xY
yMn
2-yO
4, Y=0～0.1 wherein.
In the step 1 of the above-mentioned method for preparing lithium manganese oxide, organic acid can be oxalic acid, citric acid, acrylic acid,, benzoic acid, fumaric acid, tartaric acid or malonic acid, the alcohol of solid phase can be pentaerythrite, and sugar can be sucrose or glucose, and amino acid can be glutamic acid.
Synthetic method of the present invention is without any need for solvent, and reaction condition is simple, and is easy to operate, raw materials used cheap.Therefore method of the present invention is a kind of pollution-free, low-cost, safety easily row prepare the method for positive pole of lithium manganese battery material lithium manganese oxide by lithium manganese salt.And product purity is very high, and productive rate is also generally more than 95%.
Method of the present invention has adopted low temperature Solid complexing reaction method, utilizes organic substance and lithium, manganese salt to form the complexing intermediate earlier, and calcining can make lithium salts and manganese salt generate the LiMn of spinel-type at a lower temperature again
2O
4LiMnO with stratiform
2This method has kept traditional high temperature solid state reaction advantages of simple operation, and it is low to possess the synthesis temperature that high temperature solid state reaction do not possess simultaneously, the characteristics that the reaction time is short.
The present invention has adopted the organic substance of number of different types to replace organic acid as reducing agent and dispersant, earlier and lithium salts, manganese salt mixed grinding form intermediate, dry under the low-heat presoma, calcine again and obtain end-product.Detect by XRD, products therefrom is the LiMn of pure spinel-type just
2O
4LiMnO with stratiform
2(, can obtain two kinds of products) with method by changing the stoichiometric proportion of raw material.
The present invention is also with Cr and the Y two metal ion species Li that mixes spinel-type by this solid reaction process success
xMn
2O
4In.The metering of Li, Mn, each metal ion such as Cr, Y is than can recently regulating control by the metering of reactant in the product simultaneously, i.e. the metering of each metal ion of reaction front and back is than identical, so the value that can regulate x, y easily, to obtain optimal proportion.This through the improved Li of overdoping
1+xM
yMn
2-yO
4Can improve Li greatly
1+xMn
2O
4The electrochemistry cycle performance.
Four, description of drawings
Fig. 1 is the various Li of different organic substance preparations
1+xMn
2O
4The XRD diffraction spectrogram, wherein:
A: by the Li of embodiment 1 method preparation
1+xMn
2O
4
B: by the Li of embodiment 2 preparations
1+xMn
2O
4
C: by the Li of embodiment 6 preparations
1+xCr
yMn
2-yO
4
D: by the Li of embodiment 7 preparations
1+xY
yMn
2-yO
4
E: by the Li of embodiment 3 preparations
1+xMn
2O
4
F: by the Li of embodiment 4 preparations
1+xMn
2O
4
G: by the Li of embodiment 8 preparations
1+xCr
yMn
2-yO
4
H: by the Li of embodiment 9 preparations
1+xY
yMn
2-yO
4
Fig. 2 is the Li of different organic substance preparations
1+xMnO
2The XRD diffraction spectrogram, wherein:
A: by the Li of oxalic acid preparation
1+xMnO
2B: by the Li of glucose preparation
1+xMnO
2
Fig. 3 is xps energy spectrum figure: Li
1+xCr
yMn
2-yO
4In the Mn2P spectrogram.
Fig. 4 is xps energy spectrum figure: Li
1+xMnO
2Middle Mn2P spectrogram.
Five, embodiment
Further specify method of the present invention by the following examples.
1, the Li for preparing pure spinel-type
1+xMn
2O
4
Embodiment 1. takes by weighing 0.5 gram lithium acetate, 2.2 gram manganese acetates and 2.1 gram oxalic acid respectively, grinds about one hour at agate mortar, and three kinds of materials are fully mixed.With this mixture in 80 ℃ of following intensive dryings, abundant this intermediate product of porphyrize again.Place crucible to calcine about 12 hours down at last, obtain the Li of the rich lithium-spinel type of black in 850 ℃
1+xMn
2O
4
Embodiment 2.Take by weighing 0.5 gram lithium acetate, 2.2 gram manganese acetates and 0.7 gram oxalic acid respectively, ground about one hour, three kinds of materials are fully mixed at agate mortar.With this mixture in 75 ℃ of following intensive dryings, abundant this intermediate product of porphyrize again.Place crucible to calcine about 12 hours down at last, obtain the Li of the rich lithium-spinel type of black in 600 ℃
1+xMn
2O
4
Embodiment 3. takes by weighing 0.5 gram lithium acetate, 2.2 gram manganese acetates and 5.7 gram sucrose respectively, grinds about one hour at agate mortar, and three kinds of materials are fully mixed.With this mixture in 80 ℃ of following intensive dryings, abundant this intermediate product of porphyrize again.Place crucible to calcine about 15 hours down at last, obtain the Li of the rich lithium-spinel type of black in 600 ℃
1+xMn
2O
4
Embodiment 4. takes by weighing 0.5 gram lithium acetate, 2.2 gram manganese acetates and 1.9 gram sucrose respectively, grinds about one hour at agate mortar, and three kinds of materials are fully mixed.With this mixture in 85 ℃ of following intensive dryings, abundant this intermediate product of porphyrize again.Place crucible to calcine about 18 hours down at last, obtain the Li of the rich lithium-spinel type of black in 550 ℃
1+xMn
2O
4
Embodiment 5. takes by weighing 0.44 gram lithium acetate, 2.2 gram manganese acetates and 3.524 gram citric acids respectively, grinds about one hour at agate mortar, and three kinds of materials are fully mixed.With this mixture in 80 ℃ of following intensive dryings, abundant this intermediate product of porphyrize again.Place crucible to calcine about 12 hours down at last, obtain the Li of the poor lithium-spinel type of black in 800 ℃
1+xMn
2O
4
Same method replaces oxalic acid, sucrose, citric acid also can obtain same product respectively with organic substances such as acrylic acid, glutamic acid, benzoic acid, malonic acid, fumaric acid, tartaric acid, glucose, pentaerythrites.
2, the Li of the spinel-type of preparation doping
1+xM
yMn
2-yO
4
Embodiment 6. takes by weighing 0.44 gram lithium acetate, 2.113 gram manganese acetates, 0.067 gram chromium carbonate and 2.283 gram pentaerythrites respectively and grinds (it is better that milling time prolongs effect slightly) with example 1 method, 80 ℃ of dry back gained mixture porphyrizes are placed in the crucible, calcining got the product of black in about 16 hours under 600 ℃, was the Li of doped spinel type
1+xCr
yMn
2-yO
4
Embodiment 7. takes by weighing 0.42 gram lithium acetate, 2.178 gram manganese acetates, 0.01 gram three yittrium oxide and 2.517 gram tartaric acid respectively and grinds with embodiment 6 methods, 80 ℃ of dry back gained mixture porphyrizes are placed in the crucible, calcining got the product of black in about 16 hours under 600 ℃, for mixing the Li of spinel-type
1+xY
yMn
2-yO
4
Embodiment 8. takes by weighing 0.50 gram lithium acetate, 2.178 gram manganese acetates, 0.027 gram chromium carbonate and 1.75 gram malonic acid respectively and grinds with embodiment 6 methods, dry back gained mixture porphyrize is placed in the crucible, calcining got the product of black in about 16 hours under 600 ℃, for mixing the Li of spinel-type
1+xCr
yMn
2-yO
4
Embodiment 9. takes by weighing 0.42 gram lithium acetate, 2.178 gram manganese acetates, 0.01 gram three yittrium oxide and 3.3 gram glucose respectively and grinds with embodiment 6 methods, 80 ℃ of dry back gained mixture porphyrizes are placed in the crucible, calcining got the product of black in about 16 hours under 600 ℃, for mixing the Li of spinel-type
1+xY
yMn
2-yO
4
Same method replaces pentaerythrite, tartaric acid, malonic acid also can obtain same product respectively with organic substances such as oxalic acid, citric acid, acrylic acid, glutamic acid, benzoic acid, fumaric acid, sucrose, glucose.
The XRD diffraction spectrogram of gained portion of product is seen Fig. 1.
By the XRD spectra of Fig. 1 as can be known embodiment 1～9 can obtain the Li of pure spinel-type
1+xMn
2O
4, and structure does not change after two kinds of ions of Cr, Y mixing respectively, adopts aforementioned 11 kinds of organic substances all can obtain identical result yet.But sample and unadulterated comparing after mixing, its each diffraction peak intensity is lower, illustrates that crystallinity is poor slightly.Calcining heat also has a significant impact the granular size and the crystallinity of sample, and under the identical time, the high more then products therefrom of calcining heat particle is big more, and crystallinity is also good more.
3, the Li for preparing pure stratiform
1+xMnO
2
Embodiment 10. takes by weighing 0.5 gram lithium acetate respectively, 1.1 gram manganese acetates and 1.409 restrain oxalic acid, is placed in the crucible with the grinding of embodiment 1 method, dry back gained mixture porphyrize, calcines about 18 hours down in 450 ℃, obtains the bronzing product, is the stratiform Li of rich lithium
1+xMnO
2
Embodiment 11. takes by weighing 0.44 gram lithium acetate respectively, 1.1 gram manganese acetates and 2.215 restrain glucose, is placed in the crucible with the grinding of example 1 method, dry back gained mixture porphyrize, calcines about 18 hours down in 450 ℃, obtains the bronzing product, is the stratiform Li of poor lithium
1+xMnO
2
Same method replaces oxalic acid and glucose also can obtain same product respectively with organic substances such as citric acid, acrylic acid, glutamic acid, benzoic acid, malonic acid, fumaric acid, tartaric acid, sucrose, pentaerythrites.
The Li that the inventive method makes
1+xMnO
2The XRD diffraction spectrogram see Fig. 2.
Fig. 2 and stratiform LiMnO
2Standard spectrogram basically identical, illustrate that products therefrom is exactly the LiMnO of stratiform
2
Adopt aforementioned 11 kinds of organic substances to make complexing agent and all can obtain same result.
Remarks: the Li of spinel-type
1+xMn
2O
4Li with stratiform
1+xMnO
2The figure basically identical of XRD standard spectrogram, but the latter to go out the peak angle bigger, the test gained is the result be consistent with it.
Embodiment 12.XPS spectrum analysis
Shown in Fig. 3,4: at Li
1+xCr
yMn
2-yO
4In, the electronics binding capacity 642.05eV of Mn2P3/2, Li
1+xMnO
2The electronics binding capacity of middle Mn2P3/2 is 641.8eV (with the numerical value after the charcoal calibration just, as follows).And MnO
2The electronics of middle Mn2P3/2 is in conjunction with being changed to 642.2eV, Mn
2O
3The electron binding energy of middle Mn2P3/2 is 641.7eV, Li
1+xCr
yMn
2-yO
4The peak width of middle Mn2P is also than Li
1+xMnO
2In big many of the peak width of Mn2P, so it has the Mn of trivalent and tetravalence two states as can be known, wherein tetravalence manganese content is more.This is to replace Mn because excessive lithium enters the octahedra 16d of spinelle position
3+, Mn
4+Concentration also to increase accordingly keeping charge balance, thereby improved the average valence of manganese, the valent raising of manganese also can effectively prevent the generation of Jahn-Teller effect, improves its cycle performance.From Cr2P can spectrogram as can be known, itself and chromic standard spectrogram meet fully, so Li
1+xCr
yMn
2-yO
4In Cr be trivalent.
Li
1+xMnO
2The electron binding energy of middle Mn2P3/2 is 641.8eV, meets substantially with manganic position, and peak width is little, should be the manganic of single valence.
The elementary analysis of embodiment 13. lithium manganese oxides
Table 1 is the ICP results of elemental analyses
The content of Li, Mn, elements such as Cr, Y in the different samples of table 1
A:, calcine 10h gained Li down in 600 ℃ again by the oxalic acid preparation
1+xCr
yMn
2-y0
4B:, calcine 16h gained Li down in 600 ℃ again by the glucose preparation
1+xCr
yMn
2-yO
4C:, calcine 16.5h gained Li down in 600 ℃ again by the glucose preparation
1+xY
yMn
2-yO
4D:, calcine 18h gained Li down in 450 ℃ again by the oxalic acid preparation
1+xMnO
2Remarks: the raw materials used chemical dosage ratio of each sample is different.As shown in Table 1: Cr and Y two metal ion species are by the Li that mixes spinel-type of this solid reaction process success
xMn
2O
4In.The molar fraction of Li, Mn, metal ions such as Cr, Y is than regulating by the ratio of reactant in the product simultaneously, and promptly the ratio of each metal ion is identical before and after the reaction, so the value that can regulate x, y easily, to obtain optimal proportion.This through the improved Li of overdoping
1+xM
yMn
2-yO
4(M is other metallic element, and is as follows) can improve Li greatly
1+xMn
2O
4The electrochemistry cycle performance.
| Title | ????Li | ????Mn | ????Cr | ????Y |
| ????A | ????3.83％ | ????53.3％ | ????2.62％ | ????0 |
| ????B | ????3.6％ | ????57％ | ????2.6％ | ????0 |
| ????C | ????3.6％ | ????61％ | ????0 | ????0.94％ |
| ????D | ????6.21％ | ????46％ | ????0 | ????0 |
Claims (6)
1. a low fever solid phase reaction prepares the method for lithium manganese oxide, it is characterized in that it is made up of the following step:
Step 1, the organic acid of lithium acetate, manganese acetate and solid phase or alcohol or sugar or amino acid are mixed by stoichiometric proportion, at room temperature grind, so that mixture mixes, the ratio of their amount of substances is: (lithium+manganese): organic substance=1: 0.4～1: 2
Step 2, mixture that step 1 is obtained after 75～85 ℃ of dryings, 350～850 ℃ down calcining promptly obtained end product Li in 12～18 hours
1+xMn
2O
4Or Li
1+xMnO
2, wherein X=-0.1～+ 0.2 according to the stoichiometric proportion difference, obtains the LiMn of spinel-type
2O
4Or the LiMnO of stratiform
2
2. the method for preparing lithium manganese oxide according to claim 1 is characterized in that the ratio of their amount of substances is: (lithium+manganese): organic substance=1: 1～1.2.
3. the method for preparing lithium manganese oxide according to claim 1 is characterized in that preparing the LiMn of spinel-type
2O
4Calcining heat be 550 ℃-600 ℃.
4. the method for preparing lithium manganese oxide according to claim 1 is characterized in that preparing the LiMnO of stratiform
2Calcining heat be 400 ℃-450 ℃.
5. the method for preparing lithium manganese oxide according to claim 1, it is characterized in that: organic acid be oxalic acid, citric acid, acrylic acid,, benzoic acid, fumaric acid, tartaric acid or malonic acid, the alcohol of solid phase is pentaerythrite, and sugar is sucrose or glucose, and amino acid is glutamic acid.
6. the method for preparing lithium manganese oxide according to claim 1 is characterized in that: at preparation LiMn
2O
4Step 1 in, can in lithium acetate and manganese acetate, add the chromium carbonate or three yittrium oxide of stoichiometric proportion, the end product that obtains is Li
1+xCr
yMn
2-yO
4Or Li
1+xY
yMn
2-yO
4, Y=0～0.1 wherein.
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| CN102064317A (en) * | 2009-11-13 | 2011-05-18 | 深圳市比克电池有限公司 | LiFe1-xMxPO4 compound containing carbon element and preparation method thereof |
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| CN102064317A (en) * | 2009-11-13 | 2011-05-18 | 深圳市比克电池有限公司 | LiFe1-xMxPO4 compound containing carbon element and preparation method thereof |
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