CN102064317A - LiFe1-xMxPO4 compound containing carbon element and preparation method thereof - Google Patents
LiFe1-xMxPO4 compound containing carbon element and preparation method thereof Download PDFInfo
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- CN102064317A CN102064317A CN2009101101973A CN200910110197A CN102064317A CN 102064317 A CN102064317 A CN 102064317A CN 2009101101973 A CN2009101101973 A CN 2009101101973A CN 200910110197 A CN200910110197 A CN 200910110197A CN 102064317 A CN102064317 A CN 102064317A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 10
- 229910052799 carbon Inorganic materials 0.000 title claims description 10
- 229910011902 LiFe1-xMxPO4 Inorganic materials 0.000 title abstract 4
- 229910010595 LiFe1−xMxPO4 Inorganic materials 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 206010037660 Pyrexia Diseases 0.000 claims description 17
- 238000003746 solid phase reaction Methods 0.000 claims description 17
- 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 13
- 239000008103 glucose Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 229910011570 LiFe 1-x Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 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 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910010710 LiFePO Inorganic materials 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003836 solid-state method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a new compound LiFe1-xMxPO4/C, wherein M is Mn, Co, Ni, Al or V, and x is no less than 0 and no more than 1. The invention also discloses a lithium ion battery positive electrode material containing the new compound and a preparation method of the compound. The LiFe1-xMxPO4/C compound disclosed by the invention has excellent electrochemistry performance, is prepared by adopting a low thermosetting phase reaction method, the process is simple,the synthesis temperature is lower, the price of the used material is low, and the compound LiFe1-xMxPO4/C is convenient for large-scale production.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly relate to a kind of LiFe
1-xM
xPO
4/ C compound, its preparation method and in lithium rechargeable battery as the application of positive electrode.
Background technology
Lithium rechargeable battery have have extended cycle life, plurality of advantages such as the big and memory-less effect of discharging voltage balance, specific capacity, make it more and more be subjected to the public's concern and favor in the extensive use of numerous areas such as mobile phone, notebook computer and portable electronic device.Along with the development of mixed power electric car and secondary cell electric automobile, the capacity and the quality of rechargeable battery were had higher requirement in recent years.
LiFePO with olivine structural
4Be the existing compound of occurring in nature,, be expected to become anode material for lithium-ion batteries of new generation because of its multiplying power and security performance with stable structure, excellence.
1997, people such as Goodenough in patent WO9740541, reported the LiFePO for preparing in the inert atmosphere first
4The chemical property of compound, thus people's common concern caused.Prepare LiFePO at present
4The method of compound mainly is high temperature solid-state method (dry method) and some solwution methods (wet method), as sol-gel process, and coprecipitation, hydro thermal method or the like.The major defect of these methods is exactly that operation is loaded down with trivial details, and particularly conventional solid-state method has high-temperature, and the shortcoming of long-time and high energy consumption has so just been brought very big drawback to industrial production.
The low-heat solid phase method is used as metal-organic preparation (Braga, D., Chemical Review, 92 (1992) 633-665 the earliest as a kind of softening method; Zhu, M., Li, Y.R., Luo, J.and Zhou X.G., Chinese Science Bulletin, 48 (2003) 2041-2043; CN1068811A).This method progressively is applied to the preparation process of inorganic material at present.Wherein CN03131933.5 discloses the method that a kind of low fever solid phase reaction prepares lithium manganese oxide; CN200510011676.1 discloses a kind of method that adopts low fever solid phase reaction to prepare laminar oxide material of lithium, cobalt, nickel and manganese; CN200510086505.5 then discloses the method for utilizing low fever solid phase reaction to prepare Li, Ni, Mn oxide material.But for LiFePO
4The class material is not at present as yet relevant for the bibliographical information that adopts the low fever solid phase reaction method to be prepared.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of LiFe of new carbon elements is provided
1-xM
xPO
4Compound (LiFe
1-xM
xPO
4/ C) and contain the lithium ion secondary battery anode material of this compound.
Still a further object of the present invention provides above-mentioned LiFe
1-xM
xPO
4Simple, the preparation method of being convenient to large-scale production of/C compound.
For achieving the above object, the invention provides a kind of new compound: the LiFe of carbon elements
1-xM
xPO
4(LiFe
1-xM
xPO
4/ C), M is Mn, Co, Ni, Al or V, 0≤x≤1.
C connects by weak interaction force, chemical bond key and/or carbon mixes and LiFe
1-xM
xPO
4Link to each other, and preferred 0＜x＜0.2.
The present invention also provides the anode material for lithium-ion batteries that contains above-claimed cpd.
The present invention further provides the above-mentioned LiFe of preparation
1-xM
xPO
4The method of/C compound, described method are the low fever solid phase reaction method, and described method comprises:
The preparation of predecessor:
A, with the oxide of organic acid molysite or ferrous salt, Li source compound, oxalic acid, phosphate and M element or acetate according to Li: Fe: H
2C
2O
4: M: PO
4=a: 1-x: 1: x: 1 ratio also adds organic substance and is mixed together evenly, wherein 1＜a＜1.1;
B, under 60 ℃～120 ℃ temperature conditions, carry out low fever solid phase reaction 3～6h and obtain predecessor;
The preparation of compound:
C, sintering obtained end-product in 5～14 hours under 550 ℃～800 ℃ and inert atmosphere.
Among the step a:
Described organic acid molysite or ferrous salt are preferably the molysite or the ferrous salt of citric acid or oxalic acid;
Described Li source compound is preferably carbonate or the hydroxide of Li;
Described phosphate is preferably ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate;
Described organic substance comprises at least a in polyethylene, dextrin, sucrose, glucose, starch and the phenolic resins;
Organic addition is the theoretical LiFe of generation
1-xM
xPO
4Weight 8%～35%.
In the preferred embodiment of the present invention, described step b further comprises, before the low fever solid phase reaction, adds appropriate amount of deionized water in the product that step a mixes, and dries after low fever solid phase reaction.
Among the step c, described inert atmosphere is preferably nitrogen or argon gas atmosphere.
Owing to adopted above technical scheme, the beneficial effect that the present invention is possessed is:
LiFe of the present invention
1-xM
xPO
4/ C compound has excellent chemical property, has higher electronic conductivity, when it is used as lithium ion secondary battery anode material, has higher specific capacity and cycle efficieny.
The present invention adopts the low fever solid phase reaction legal system to be equipped with LiFe
1-xM
xPO
4/ C compound, with respect to conventional solid-state method, this method need not to carry out long-time grinding the in early stage, has lower calcination temperature and short reaction time simultaneously in the preparation process of material.This procedure is simple, and synthesis temperature is lower, and material therefor is cheap, is convenient to large-scale production.
Description of drawings
Fig. 1 is LiFePO prepared among the embodiment 1
4The XRD spectra of/C compound;
Fig. 2 is LiFePO prepared among the embodiment 2
4The XRD spectra of/C compound;
Fig. 3 is LiFe prepared among the embodiment 3
0.99Ni
0.01PO
4The XRD spectra of/C compound;
Fig. 4 is LiFe prepared among the embodiment 4
0.97Ni
0.03PO
4The XRD spectra of/C compound;
Fig. 5 is LiFe prepared among the embodiment 5
0.89Co
0.11PO
4The XRD spectra of/C compound;
Fig. 6 is LiFe prepared among the embodiment 6
0.95Al
.0.05PO
4The XRD spectra of/C compound;
Fig. 7 is LiFe prepared among the embodiment 7
0.85V
.0.15PO
4The XRD spectra of/C compound;
Fig. 8 is LiFePO prepared in embodiment 1 and 2
4The first charge-discharge curve of/C compound;
Fig. 9 is the LiFe for preparing respectively among the embodiment 3,4,5
0.09Ni
0.01PO
4/ C compound, LiFe
0.97Ni
0.03PO
4/ C compound and LiFe
0.89Co
0.11PO
4The first charge-discharge curve of/C compound;
Figure 10 is the prepared LiFe of embodiment 6
0.95Al
.0.05PO
4The first charge-discharge curve of/C compound;
Figure 11 is the prepared LiFe of embodiment 7
0.85V
.0.15PO
4The first charge-discharge curve of/C compound.
Embodiment
At LiFePO
4In the structure, Fe and Li constitute FeO respectively
6And LiO
6Octahedron, P then form PO
4Tetrahedron.Adjacent FeO
6The octahedra FeO that on the bc face, has formed a Z word structure by a shared O atom
6Layer.In charge and discharge process, Li
+Ion can take off in reversible embedding, corresponding to Fe
3+/ Fe
2+Mutual conversion, platform voltage is 3.50V, and platform is more steady.Because the bond energy of P-O key is very big, PO
4Thereby can to play the support structure effect highly stable for inertia in the removal lithium embedded process for tetrahedron.Simultaneously, also just because of adjacent FeO
6Octahedra by summit connection altogether, hindered Li to a certain extent
+Freely spreading of ion, finally caused lower electronic conductivity (Thackeray, M., Lithium-ion batteries:An unexpected conductor.Nat Mater2002,1, (2), 81-82.), in order fundamentally to solve the lower electronic conductivity of material, we have synthesized LiFe
1-xM
xPO
4/ C material, M is divalence or Tricationic in this material, and radius is less than Fe
2+, in this compound by its MO that forms
6Thereby octahedron will occupy less relatively space and help Li
+Therefore freely spreading of ion can fundamentally improve LiFePO
4The electronic conductivity of material improves the telephony performance of material.
Noval chemical compound LiFe of the present invention
1-xM
xPO
4Among/the C, M is Mn, Co, Ni, Al or V, 0≤x≤1, preferred 0＜x＜0.2.C atom and LiFe in this compound
1-xM
xPO
4Mainly between the compound connect, also can exist the carbon of a little to mix simultaneously, so just make LiFe by weak interaction force and chemical bond key
1-xM
xPO
4/ C compound has traditional relatively LiFePO
4The conductivity that compound is more excellent, thus make material more be applicable to lithium ion conventional batteries and electrokinetic cell field.
Noval chemical compound LiFe of the present invention
1-xM
xPO
4/ C possesses excellent chemical property, can be used as the positive electrode of lithium ion battery, and has higher specific capacity and cycle efficieny.
Noval chemical compound LiFe of the present invention
1-xM
xPO
4The preparation method of/C is to adopt the low fever solid phase reaction that is different from the conventional high-temperature solid phase method.With respect to conventional solid-state method, method of the present invention need not to carry out long-time grinding the in early stage, has lower calcination temperature and short reaction time simultaneously in the preparation process of material.This procedure is simple, and synthesis temperature is lower, and material therefor is cheap, is convenient to large-scale production.
Preparation method of the present invention mainly comprises the preparation predecessor and prepares compound of the present invention by predecessor.
In the preparation process of predecessor, comprise the oxide of organic acid molysite or ferrous salt, Li source compound, oxalic acid, phosphate and M element (M is Mn, Co, Ni, Al or V) or acetate according to Li: Fe: H
2C
2O
4: M: PO
4=a: 1-x: 1: x: 1 ratio and the organic substance that adds proper proportion are mixed together evenly, must guarantee that wherein the Li element is excessive, and promptly 1＜a＜1.1 influence not quite the result when Li element consumption changes in this scope in the course of reaction.In preparation process, often select a=1.05 for use; Under 60 ℃～120 ℃ temperature conditions, carry out low fever solid phase reaction 3～6h then and obtain predecessor.
In the preparation process of predecessor, organic acid molysite or ferrous salt are preferably the molysite or the ferrous salt of citric acid or oxalic acid, more preferably use ironic citrate (C
6H
5O
7Fe5H
2O); Li source compound is preferably carbonate or the hydroxide of Li, more preferably uses LiOH; Phosphate is preferably ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate, more preferably uses ammonium dihydrogen phosphate; Organic addition is the theoretical LiFe of generation
1-xM
xPO
48%～35% of weight, and use simple organic usually, only need satisfy the simple organic that in inert environments, can decomposite organic carbon and all be applicable to the present invention, such as selecting at least a in polyethylene, dextrin, sucrose, glucose, starch and the phenolic resins for use.Before carrying out low fever solid phase reaction under 60 ℃～120 ℃ the temperature conditions, preferably in mixture, add appropriate amount of deionized water.The purpose that adds proper amount of deionized water is to provide a comparatively moist reaction environment to system, thereby helps the preparation of material." in right amount " specifically finger can observe solid particles surface a little moist getting final product is arranged, the accurate consumption of deionized water does not have particular restriction on this basis.Further oven dry promptly obtains the predecessor of The compounds of this invention after the adding deionized water carries out low fever solid phase reaction.
The predecessor for preparing sintering under 550 ℃～800 ℃ and inert atmosphere can be obtained end product LiFe in 5～14 hours
1-xM
xPO
4/ C compound.Wherein, inert atmosphere is preferably nitrogen or argon gas atmosphere.
In conjunction with the accompanying drawings the present invention is described in further detail below by specific embodiment.
Embodiment 1
With Fe: Li: H
2C
2O
4: PO
4=1: 1.05: 1: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4And NH
4H
2PO
4After mixing, add the sucrose of proper proportion again, the consumption of sucrose is the theoretical LiFePO of generation
4Quality 10%.In the product that these mix, add proper amount of deionized water then and make solid particles surface that a little humidity be arranged, oven dry obtains predecessor behind 100 ℃ of reaction 4h, with the predecessor for preparing 650 ℃ under argon gas atmosphere sintering then can obtain end product LiFePO in 8 hours
4/ C compound.
Embodiment 2
With Fe: Li: H
2C
2O
4: PO
4=1: 1.05: 1: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4And NH
4H
2PO
4After mixing, add the glucose of proper proportion again, the consumption of glucose is the theoretical LiFePO of generation
4Quality 10%.In the product that these mix, add proper amount of deionized water then, in 60 ℃ of reactions after 6 hours oven dry obtain predecessor, with the predecessor for preparing 750 ℃ under nitrogen atmosphere sintering then can obtain end product LiFePO in 6 hours
4/ C compound.
Embodiment 3
With Fe: Li: H
2C
2O
4: Ni: PO
4=0.99: 1.05: 1: 0.01: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4, nickel acetate and NH
4H
2PO
4After mixing, add the sucrose of proper proportion again, the consumption of sucrose is the theoretical LiFePO of generation
4Quality 30%.Add proper amount of deionized water then in the product that these mix, oven dry obtains predecessor behind 120 ℃ of reaction 3h, with the predecessor for preparing 550 ℃ under argon gas atmosphere sintering then can obtain end product LiFe in 12 hours
0.99Ni
0.01PO
4/ C compound.
Embodiment 4
With Fe: Li: H
2C
2O
4: Ni: PO
4=0.97: 1.05: 1: 0.03: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4, nickel protoxide and NH
4H
2PO
4After mixing, add the glucose of proper proportion again, the consumption of glucose is the theoretical LiFePO of generation
4Quality 20%.Add proper amount of deionized water then in the product that these mix, oven dry obtains predecessor behind 80 ℃ of reaction 5h, and the predecessor for preparing then can be obtained end product LiFe in 8 hours at 650 ℃ of sintering
0.97Ni
0.03PO
4/ C compound.
Embodiment 5
With Fe: Li: H
2C
2O
4: Co: PO
4=0.89: 1.05: 1: 0.11: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4, cobalt acetate and NH
4H
2PO
4After mixing, add the glucose of proper proportion again, the consumption of glucose is the theoretical LiFePO of generation
4Quality 20%.Add proper amount of deionized water then in the product that these mix, oven dry obtains predecessor behind 80 ℃ of reaction 5h, and the predecessor for preparing then can be obtained end product LiFe in 8 hours at 650 ℃ of sintering
0.89Co
0.11PO
4/ C compound.
Embodiment 6
With Fe: Li: H
2C
2O
4: Al: PO
4=0.95: 1.05: 1: 0.05: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4, Al
2O
3And NH
4H
2PO
4After mixing, add the glucose of proper proportion again, the consumption of glucose is the theoretical LiFePO of generation
4Quality 20%.Add proper amount of deionized water then in the product that these mix, oven dry obtains predecessor behind 80 ℃ of reaction 5h, and the predecessor for preparing then can be obtained end product LiFe in 8 hours at 650 ℃ of sintering
0.95Al
0.05PO
4/ C compound.
Embodiment 7
With Fe: Li: H
2C
2O
4: V: PO
4=0.85: 1.05: 1: 0.15: 1 ratio takes by weighing ironic citrate, LiOHH respectively
2O, H
2C
2O
4, vanadic oxide and NH
4H
2PO
4After mixing, add the glucose of proper proportion again, the consumption of glucose is the theoretical LiFePO of generation
4Quality 20%.Add proper amount of deionized water then in the product that these mix, oven dry obtains predecessor behind 80 ℃ of reaction 5h, and the predecessor for preparing then can be obtained end product LiFe in 8 hours at 650 ℃ of sintering
0.85V
0.15PO
4/ C compound.
Experimental example
Embodiment 1,2,3,4,5,6,7 is gained LiFe separately
1-xM
xPO
4The XRD spectral line of/C compound is respectively as Fig. 1-shown in Figure 7.The X-ray diffraction result shows the LiFe that adopts this method preparation
1-xM
xPO
4/ C compound has very high purity, does not have the appearance of other impurity peaks, therefore can be used as lithium ion secondary battery anode material.
With the X-ray diffraction result of these materials by the powder crystal software for calculation---Winplot calculates the cell parameter that can obtain these materials, cell parameter result shown in table-1, the LiFePO of preparation among the embodiment 1 and 2 as can be seen from the result
4/ C has close cell parameter.Be respectively
With
And the LiFe for preparing respectively by embodiment 3,4 and 5
0.99Ni
0.01PO
4/ C, LiFe
0.97Ni
0.03PO
4/ C and LiFe
0.89Co
0.11PO
4The compound of/C has close cell parameter equally, is respectively 292.55,292.81 and
But than pure LiFePO
4The cell parameter of/C is little, and its main cause is because the Ni of less ionic radius
2+And Co
2+Ion has occupied Fe respectively
2+Should be at LiFePO
4Position in the structure cell, thus caused the unit cell volume of embodiment 3,4 and 5 to be less than the unit cell volume of embodiment 1 and 2 prepared compounds, Comparatively speaking, the LiFe that embodiment 6 and 7 prepares
0.95Al
0.05PO
4/ C and LiFe
0.85V
0.15PO
4/ C material possesses littler unit cell volume, and main cause is owing to introduced the littler Tricationic Al of unit cell volume respectively in this two classes composite material
3+And V
3+Ion, and doping is more relatively.
The XRD structure cell result of calculation of-1 7 kind of material of table
Adopt the inventive method gained LiFe
1-xM
xPO
4The process that/C makes battery anode slurry is identical with battery anode slurry process in the prior art.
With embodiment 1 gained LiFePO
4/ C and Super P, PVDF prepare anode sizing agent according to the ratio of 80: 15: 5 (mass ratio), after mixing with machine,massing, and slurry on small-sized tensile pulp machine, pole piece uses aluminium foil (thickness 16 μ m), and the slurry surface density is 8-9mg/cm
2As to electrode, EC, EMC, DMC dissolve in the LiPF of 1mol/L at 1: 1: 1 according to volume ratio with metal Li
6In make electrolyte, be full of argon shield and H
2O, O
2All be assembled into half-cell in the glove box less than 1ppm.Half-cell is carried out the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 3.8V, and discharge is by voltage 2.0V.
Embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 gained LiFe
1-xM
xPO
4/ C compound also respectively according to said process assembling half-cell, carries out the experiment of constant current charge and discharge cycle to half-cell under above-mentioned same condition.
First circle discharges and recharges result and first circle efficient shown in table-2, as can be seen
Table-2 embodiment 1-7 first circle specific discharge capacity and first circle efficient
| Title | Specific discharge capacity mAh/g | First circle efficient (%) |
| Embodiment 1 | 126.4 | 90.2 |
| Embodiment 2 | 129.0 | 91.6 |
| Embodiment 3 | 144.1 | 96.0 |
| Embodiment 4 | 140.3 | 94.9 |
| Embodiment 5 | 142.3 | 95.3 |
| Embodiment 6 | 152.3 | 97.1 |
| Embodiment 7 | 148.1 | 95.6 |
Charge and discharge cycle experimental result such as Fig. 8-shown in Figure 11.
Among Fig. 8, the specific capacity of the cycle charging first 140.1mAh/g of embodiment 1 gained material, specific discharge capacity is 126.4mAh/g, first charge-discharge efficiency reaches 90.2%; The specific capacity of the cycle charging first 140.9mAh/g of embodiment 2 gained materials, specific discharge capacity is 129.0mAh/g, first charge-discharge efficiency reaches 91.6%.Both are comparatively approaching.
Among Fig. 9, the specific capacity of the cycle charging first 150.1mAh/g of embodiment 3 gained materials, specific discharge capacity is 144.1mAh/g, first charge-discharge efficiency reaches 96.0%; The specific capacity of the cycle charging first 147.8mAh/g of embodiment 4 gained materials, specific discharge capacity is 140.3mAh/g, first charge-discharge efficiency reaches 94.9%; The specific capacity of the cycle charging first 149.3mAh/g of embodiment 5 gained materials, specific discharge capacity is 142.3mAh/g, first charge-discharge efficiency reaches 95.3%.
Among Figure 10, the specific capacity of the cycle charging first 156.8mAh/g of embodiment 6 gained materials, specific discharge capacity is 152.3mAh/g, first charge-discharge efficiency reaches 97.1%; The specific capacity of the cycle charging first 155.0mAh/g of Figure 11 embodiment 7 gained materials, specific discharge capacity is 148.1mAh/g, first charge-discharge efficiency reaches 95.6%.
From Fig. 8, Fig. 9, Figure 10 and Figure 11 as can be known, adopt the LiFe of the inventive method gained
1-xM
xPO
4/ C has the excellent charging and discharging performance, simultaneously, prepares LiFe by this method
0.99Ni
0.01PO
4/ C, LiFe
0.97Ni
0.03PO
4/ C, LiFe
0.89Co
0.11PO
4/ C, LiFe
0.95Al
0.05PO
4/ C and LiFe
0.85V
0.15PO
4/ C compound is than unadulterated LiFePO
4/ C compound has more excellent charging and discharging performance, and its main cause may be because LiFe
0.09Ni
0.01PO
4/ C, LiFe
0.97Ni
0.03PO
4/ C, LiFe
0.89Co
0.11PO
4/ C, LiFe
0.95Al
0.05PO
4/ C and LiFe
0.85V
0.15PO
4The Ni that less ionic radius is arranged in/C the compound
2+, Co
2+, Al
3+And V
3+It is FeO originally that the introducing of ion has caused
6Octahedral smaller volume makes Li
+Ion has the diffusion space that more strengthens, thereby has excellent chemical property from the electronic conductivity that has improved compound in essence.
Above content be in conjunction with concrete execution mode to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the LiFe of carbon elements
1-xM
xPO
4Compound, M are Mn, Co, Ni, Al or V, 0≤x≤1.
2. compound according to claim 1 is characterized in that: carbon connects by weak interaction force, chemical bond key and/or carbon mixes and LiFe
1-xM
xPO
4Link to each other, and 0＜x＜0.2.
3. anode material for lithium-ion batteries, it is characterized in that: described positive electrode contains claim 1 or 2 described compounds.
4. the preparation method of claim 1 or 2 described compounds, described method is the low fever solid phase reaction method, described method comprises:
The preparation of predecessor:
A, with the oxide of organic acid molysite or ferrous salt, Li source compound, oxalic acid, phosphate and M element or acetate according to Li: Fe: H
2C
2O
4: M: PO
4=a: 1-x: 1: x: 1 ratio also adds organic substance and is mixed together evenly, wherein 1＜a＜1.1;
B, under 60 ℃～120 ℃ temperature conditions, carry out low fever solid phase reaction 3～6h and obtain predecessor;
The preparation of compound:
C, predecessor sintering under 550 ℃～800 ℃ and inert atmosphere was obtained end-product in 5～14 hours.
5. method according to claim 4 is characterized in that: among the step a, described organic acid molysite or ferrous salt are the molysite or the ferrous salt of citric acid or oxalic acid.
6. according to claim 4 or 5 described methods, it is characterized in that: among the step a, described Li source compound is carbonate or the hydroxide of Li.
7. according to any described method in the claim 4～6, it is characterized in that: among the step a, described phosphate is ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate.
8. according to any described method in the claim 4～7, it is characterized in that: among the step a, described organic substance comprises at least a in polyethylene, dextrin, sucrose, glucose, starch and the phenolic resins.
9. according to any described method in the claim 4～7, it is characterized in that: among the step a, organic addition is the theoretical LiFe of generation
1-xM
xPO
4Weight 8%～35%.
10. according to any described method in the claim 4～9, it is characterized in that: described step b further comprises, before the low fever solid phase reaction, adds entry in the product that step a mixes, and dries after low fever solid phase reaction.
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|---|---|---|---|
| CN200910110197.3A CN102064317B (en) | 2009-11-13 | 2009-11-13 | LiFe1-xMxPO4 compound containing carbon element and preparation method thereof |
| HK11111279.6A HK1157067A1 (en) | 2009-11-13 | 2011-10-20 | Carbon element included compound life1-xmxpo4 and the preparation method thereof life1-xmxpo4 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105261732A (en) * | 2015-09-02 | 2016-01-20 | 武汉理工力强能源有限公司 | Vanadium doped lithium iron phosphate/carbon three-dimensional porous electrode material and preparation method therefor |
| CN106486668A (en) * | 2016-10-14 | 2017-03-08 | 山东省科学院能源研究所 | A kind of phosphoric acid ferrimanganic vanadium presoma, phosphoric acid ferrimanganic vanadium lithium/carbon positive electrode and preparation method |
| CN109980295A (en) * | 2019-03-26 | 2019-07-05 | 陈林龙 | The preparation process of new energy resource power battery |
| CN112349904A (en) * | 2020-09-27 | 2021-02-09 | 江苏合志新能源材料技术有限公司 | Lithium ion battery multi-phosphate anode material and preparation method thereof, anode and lithium ion battery |
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| CN105261732A (en) * | 2015-09-02 | 2016-01-20 | 武汉理工力强能源有限公司 | Vanadium doped lithium iron phosphate/carbon three-dimensional porous electrode material and preparation method therefor |
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| CN106486668B (en) * | 2016-10-14 | 2019-07-16 | 山东省科学院能源研究所 | A kind of phosphoric acid ferrimanganic vanadium presoma, phosphoric acid ferrimanganic vanadium lithium/carbon positive electrode and preparation method |
| CN109980295A (en) * | 2019-03-26 | 2019-07-05 | 陈林龙 | The preparation process of new energy resource power battery |
| CN112349904A (en) * | 2020-09-27 | 2021-02-09 | 江苏合志新能源材料技术有限公司 | Lithium ion battery multi-phosphate anode material and preparation method thereof, anode and lithium ion battery |
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| Publication number | Publication date |
|---|---|
| CN102064317B (en) | 2014-11-19 |
| HK1157067A1 (en) | 2012-06-22 |
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