CN101179125A - Method of producing silicon doped LiMn2O4 lithium ion battery anode material - Google Patents
Method of producing silicon doped LiMn2O4 lithium ion battery anode material Download PDFInfo
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- CN101179125A CN101179125A CNA2007101470606A CN200710147060A CN101179125A CN 101179125 A CN101179125 A CN 101179125A CN A2007101470606 A CNA2007101470606 A CN A2007101470606A CN 200710147060 A CN200710147060 A CN 200710147060A CN 101179125 A CN101179125 A CN 101179125A
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Abstract
The invention discloses a preparation method of Si doping LiMn<SUB>2</SUB>O<SUB>4</SUB> lithium ion battery anode material. The invention is characterized in that: take manganese salt, lithium salt, and organosilane as raw materials, and take ethanol as solvent to obtain homogeneous solution of LiMn, Si according to the molar ratio(x is less than or equal to 0.1) of LiMn<SUB>2-x</SUB>Si<SUB>x</SUB>O<SUB>4</SUB>, so as to prepare uniform precursor; and then prepare Si doping LiMn<SUB>2</SUB>O<SUB>4</SUB> lithium ion battery anode material at high temperature through the method of solid-state incremental heating. The invention can settle the common problem of decreased theoretical capacity of spinel lithium manganese caused by ion doping, and the product prepared by the invention has structured crystal form, single phase, no silicon dioxide impurity and settles the difficulty of effective si- ion doping technically.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries.Especially relate to the preparation method of a kind of lithium ion battery with the ion doping LiMn2O4.
Background technology
Current, fast development along with electronics technology, make the miniaturization day by day of digitalized electron instrument, portability, as products closely bound up with our life such as mobile phone, notebook computer, MP3, so people are to the demands for higher performance of chemical power source (battery).In numerous systems, lithium ion battery with its operating voltage height, energy density advantage such as big and light weight show one's talent, be subjected to the attention of countries in the world.The global output of lithium ion battery in 2005 is 1.8 times of Ni-MH battery, and 4 times of ickel-cadmium cell are the first-selections of battery power car on the horizon.In February nineteen ninety, the rocking chair battery that the Sony company of Japan has obtained having good charge-discharge performance and higher-energy is formally released first commodity lithium ion battery to market, and its key technology is to use the reversible LiCoO that takes off embedding of lithium ion energy
2Positive electrode.The LiCoO of layer structure
2, LiNiO
2LiMn with spinel structure
2O
4Being three kinds of energy having studied can embed the positive electrode of Li at the above current potential of 3.5V, but because Co resource shortage and price are relatively costly, and the manganese aboundresources is cheap and nontoxic, environmentally friendly, so is all carrying out with LiMn energetically countries in the world
2O
4Practical research for the lithium ion battery of positive electrode.
But the LiMn of spinel structure
2O
4Irreversible capacity loss in the charge discharge process is the main cause of its development of restriction.Pure phase LiMn
2O
4The reason of irreversible capacity loss be generally considered to be because LiMn
2O
4The Jahn-Teller distortion has taken place in the crystal grain of material in charging and discharge cycles process and the dissolving of manganese ion in electrolyte solution causes structural collapse, causes thereby cause the minimizing of material active ingredient, lithium ion migrating channels to block institute.Surface modified and method ion doping all is considered to effectively to improve LiMn
2O
4The stable circulation performance of material suppresses the Jahn-Teller effect in the charge and discharge process.For example: the long seal of Tsing-Hua University ginger waits at CN1264233C and discloses a kind of method for preparing spherical LiMn2O4, think that the spherical material of preparation has improved the real density of product, can effectively improve its cyclical stability, and for further modification and modification provide advantage.The Tang Zhiyuan of University Of Tianjin etc. are at " Chinese Journal of Inorganic Chemistry ", 2006,22 (5): 890-894 has reported to utilize and has generated silicon-rich layer on the LiMn2O4 surface and reach and reduce the erosion of electrolyte to active material, suppressed the dissolving of material surface, thereby obviously improve its electrochemical heat stability.And also have a lot of different explanations for the mechanism of ion doping modification.Xie Yanting etc. are at " Solid State Ionics ", 2005,176:2563-2569 has reported the Sc element doping of rare earth element intermediate ion radius minimum, M-O bond energy maximum stabilizing effect the best to material, discharges and recharges the back capacity fully and still remains on 120mAh/g for 30 times; CN1773749A also discloses a kind of preparation method of Sc doped spinel type lithium manganate cell positive electrode material, illustrates that stabilizing ion mixes to the stabilization of LiMn2O4 lattice.CN1921184A then discloses the method for utilizing the polybasic ion doping to prepare ion doping lithium manganate cathode active material, think that the doping of polybasic ions such as Cr, Al, Mg, Ti, Zr also helps to suppress the irreversible capacity decay of lithium manganate material, 55 ℃ high temperature discharge capacity first reaches 118mAh/g, and 100 circulation volume decay are minimum to reach 8%.
What deserves to be mentioned is; above-mentioned common dopant ion; although particularly average valence, the inhibition Jahn-Teller distortion of the dopant ion of trivalent to improving manganese; thereby the lattice structure aspect of stable spinel LiMn2O4 is very favourable; but can cause the theoretical capacity of dopant material to descend usually, become the unfavorable factor of synthetic high power capacity positive electrode.And the nondecreasing Li doped Mn of design blending theory capacity
2O
4Positive electrode (such as: LiMn
1.5Ni
0.5O
4, cell voltage is near 5V) and become the important topic in the LiMn2O4 doping vario-property research naturally.
Summary of the invention
The present invention is that disclosed in order to solve unfavorable factor that common ion doping causes that the spinelle manganic acid lithium material theoretical capacity reduces a kind of what can overcome above-mentioned defective is that dopant ion prepares Si Li doped Mn with tetravalence Si ion
2O
4The anode material for lithium-ion batteries method.
In order to realize stable spinel-type LiMn
2O
4Crystal structure suppresses the irreversible capacity loss in its cycle charge discharge electric process, does not influence the purpose of the theoretical capacity of this material simultaneously, and the present invention has designed utilization+4 valency metals or nonmetal replacement spinel-type LiMn
2O
4In the manganese of inactive+4 valencys, obtain the compound of spinel structure, thereby under the situation that does not influence the theoretical capacity decay, can stablize LiMn
2O
4Lattice structure.Select the tetravalence element silicon mainly to be as doped chemical because: 1. element silicon is the quadrivalent element of valence stability, substitutes LiMn in the doping process
2O
4Nonactive tetravalence manganese ion in the structure can not cause the minimizing of active manganic ion in the structure; 2. the silicon atom amount can reduce the molecular weight of material less than the atomic weight of manganese after the doping, and the reversible active lithium ion concentration that takes off embedding is improved relatively, increases theoretical capacity; 3.Si-O key is bigger comparatively speaking, is doped with to help stablize its lattice structure, 4. nontoxic, pollution-free, the cheap material cost that can not cause of element silicon raises.But the modal raw material of element silicon is a silicon dioxide, and chemical property own is stable, destroys its stable lattice structure in case form then be difficult to, and silicon ion is effectively mixed enter the spinel lithium manganate skeleton, and itself also is not easy.Therefore Many researchers has adopted silica surface to coat the thinking of improving the LiMn2O4 cyclical stability.
To achieve these goals, effective doping of realization silicon ion, the present invention are by the following technical solutions: will analyze pure lithium salts and manganese salt, Li/Mn=1/2 is dissolved in the absolute ethyl alcohol in molar ratio, gets clear solution; The organosilan dilution is dissolved in the weak solution that gets specific concentrations in the ethanol; The ratio of Li: Mn: Si=1: 2-x: x (x≤0.1) in molar ratio in Li, Mn mixed solution under agitation adds organosilan solution then, is clear solution after mixing.Under infrared lamp, heating is also deviate from solvent gradually, the dry Gel Precursor that generates white then; The gained presoma is warming up to 300～500 ℃ of insulations 3～8 hours with 5～10 ℃/minute heating rate, and making raw material predecomposition is the amorphous mixed oxide of Li, Mn, Si, is chilled to room temperature naturally, take out grind abundant; The predecomposition product is risen to 600-1000 ℃ with 5～10 ℃/minute heating rate, be incubated 8-20 hour and make Li, Mn, the abundant crystallization of Si, then product is chilled to room temperature naturally, take out and promptly get Si Li doped Mn after grinding
2O
4Anode material for lithium-ion batteries.
Beneficial effect of the present invention and advantage:
1. this method adopts the organosilicon raw material that are easy to pyrolysis as the doped silicon source, has avoided utilizing the silicon dioxide of stable performance to cause silicon ion can not enter the shortcoming of LiMn2O4 lattice structure as raw material, thereby has realized the silicon doping purpose;
2. this method is dissolved in ethanolic solution with organosilan, gets the weak solution of specific concentrations, to help accurately quantitatively adding of Trace Silicon element;
The present invention will analyze pure lithium salts and manganese salt in molar ratio Li/Mn=1/2 also be dissolved in the absolute ethyl alcohol clear solution, to help fully mixing of organosilicon and Li, Mn element, generate the solution of homogeneous phase, obtain the presoma of Li, Mn, the mixing of Si molecular level, to help the most effective LiMn2O4 lattice that incorporates of silicon ion;
4. the technological reaction that adopts among the present invention is controlled easily, is beneficial to suitability for industrialized production, and alcohol solvent can design appropriate process and repeat to recycle, and reduces cost;
5. the silicon doping lithium manganate having spinel structure material crystals crystalline form for preparing of this method is regular, the product thing is mutually single, does not have silicon dioxide impurity phase, has broken through silicon ion technically and often has been difficult to realize a difficult problem of mixing.
Accompanying drawing 1 crystallization temperature is incubated 10h gained silicon doping LiMn2O4 product X-ray powder diffraction pattern down for 700 ℃
Accompanying drawing 2 crystallization temperatures are incubated 10h gained silicon doping LiMn2O4 product X-ray powder diffraction pattern down for 800 ℃
Accompanying drawing 3 crystallization temperatures are incubated 10h gained silicon doping LiMn2O4 product electron scanning micrograph down for 800 ℃
Embodiment
Specify the present invention by the following examples, but the present invention is not limited to these embodiment.
The morphology observation of related silicon doping lithium manganate material all adopts the JSM-5610LV scanning electron microscopy of Japanese JEOL company in following examples, and the thing identification of phases is all adopted the Japanese D/max-2500VPC of company of science to change target X-ray powder diffraction instrument and measured.
Embodiment 1:
The ratio of Li/Mn=1/2 in molar ratio, take by weighing analyze pure lithium nitrate 0.6894g and manganese acetate 4.7793g be dissolved in the 20ml absolute ethyl alcohol clear solution, then according to mol ratio Li: Mn: Si=1: 1.92: 0.02 ratio pipettes the tetramethylsilane ethanolic solution that 4 milliliters of 0.05mol/L have prepared, under agitation dropwise add in Li, the Mn mixed solution, be clear solution after mixing; Under infrared lamp, heating is also deviate from alcohol solvent gradually, the dry Gel Precursor that generates white then; The gained presoma is warming up to 400 ℃ of insulations 5 hours with 5 ℃/minute heating rate, and making raw material predecomposition is the amorphous mixed oxide of Li, Mn, Si, is chilled to room temperature naturally, take out grind abundant; Again the predecomposition product is risen to 700 degree with 5 ℃/minute heating rate, be incubated 10 hours and make Li, Mn, the abundant crystallization of Si, then product is chilled to room temperature naturally, promptly get final sample after taking out grinding.
Among the embodiment X-ray powder diffraction measurement result of gained sample as shown in Figure 1, the product crystallization is better, does not have SiO
2Diffraction maximum occur, illustrate that the Si ion doping has entered LiMn
2O
4Lattice structure in.
Embodiment 2:
In molar ratio Li/Mn=1/2 take by weighing analyze pure lithium acetate 1.0201g and manganese acetate 4.7793 be dissolved in the 20ml absolute ethyl alcohol clear solution, then according to mol ratio Li: Mn: Si=1: 1.95: 0.05 ratio pipettes the vinyltriethoxysilane ethanolic solution that 5.26 milliliters of 0.095mol/L have prepared, under agitation dropwise add in Li, the Mn mixed solution, be clear solution after mixing; Under infrared lamp, heating is also deviate from alcohol solvent gradually, the dry Gel Precursor that generates white then; The gained presoma is warming up to 400 ℃ of insulations 4 hours with 5 ℃/minute heating rate, and making raw material predecomposition is the amorphous mixed oxide of Li, Mn, Si, is chilled to room temperature naturally, take out grind abundant; Again the predecomposition product is risen to 800 degree with 5 ℃/minute heating rate, be incubated 10 hours and make Li, Mn, the abundant crystallization of Si, then product is chilled to room temperature naturally, take out the LiMn that promptly gets Si doping x=0.05 after the grinding
1.95Sio
0.05O
4Anode material for lithium-ion batteries.
Gained LiMn among the embodiment
1.95Si
0.05O
4The powder diagram of material as shown in Figure 2, the result shows the LiMn of gained sample and standard
2O
4Unanimity as a result, degree of crystallinity better, no any dephasign appearance; The sem observation result as shown in Figure 3, silicon doping LiMn
1.95Si
0.05O
4The material crystals crystalline form is regular, can find out the octahedral fustigatio external form of rule, and particle diameter is even, narrow size distribution; Illustrate that silicon doping is respond well, accomplish the end in view.
Claims (6)
1. Si Li doped Mn
2O
4The preparation method of anode material for lithium-ion batteries, its technical process comprises:
(1) will analyze pure lithium salts and manganese salt is dissolved in the absolute ethyl alcohol according to mol ratio Li/Mn=1/2;
(2) organosilan is dissolved in ethanolic solution, the concentration of preparation is at the silane ethanolic solution of 0.05-0.15mol/L;
(3) in the Li in (1), the Mn mixed solution, the ratio of Li: Mn: Si=1: 2-x: x (x≤0.1) adds the organosilan ethanolic solution in (2) in molar ratio, mixes to be clear solution.Under infrared lamp, heating is also deviate from solvent gradually, the dry Gel Precursor that generates white then;
(4) the gained raw material is warming up to 300～500 ℃ of insulations 3～8 hours with 5～10 ℃/minute heating rate, making raw material predecomposition is the amorphous mixed oxide of Li, Mn, Si, is chilled to room temperature naturally, take out grind abundant;
(5) the predecomposition product is risen to the 600-1000 degree with 5～10 ℃/minute heating rate, be incubated 8-20 hour and make Li, Mn, the abundant crystallization of Si, then product is chilled to room temperature naturally, take out and promptly get Si Li doped Mn after grinding
2O
4Anode material for lithium-ion batteries.
2. preparation method according to claim 1 is characterized in that: the lithium salts in the step (1) is lithium acetate and lithium nitrate, and manganese salt is manganese acetate and manganese nitrate.
3. preparation method according to claim 1 is characterized in that: the organosilan in the step (2) is any one in tetramethylsilane, vinyltriethoxysilane, methyltrimethoxy silane, methyl triacetoxysilane, chain alkyl trimethoxy silane, octyltri-ethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, the octadecyl trimethoxy silane;
4. preparation method according to claim 1 is characterized in that: the organosilan additional proportion in the step (3) is Li: Mn: Si=1: 2-x: x;
5. preparation method according to claim 1 is characterized in that: the predecomposition condition in the step (4) is 350～450 ℃ of insulations 3～8 hours;
6. preparation method according to claim 1 is characterized in that: step (5) product crystallization condition is 600-1000 ℃, is incubated 8-20 hour.
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Cited By (6)
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| CN102530908A (en) * | 2011-12-10 | 2012-07-04 | 桂林理工大学 | Method for preparing silicon doping phosphate manganese lithium lithium-ion battery positive electrode material by sol-gel method |
| CN102769136A (en) * | 2012-07-31 | 2012-11-07 | 山东齐星新材料科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103794775A (en) * | 2014-01-24 | 2014-05-14 | 国家纳米科学中心 | Preparation method of positive electrode material of iron-doped lithium manganate acid lithium ion battery |
| CN107946583A (en) * | 2017-12-11 | 2018-04-20 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery LiMn2O4 composite material |
| CN108054363A (en) * | 2017-12-11 | 2018-05-18 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery boron, aluminium adulterated lithium manganate composite material |
| CN113937307A (en) * | 2021-09-10 | 2022-01-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
Family Cites Families (2)
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| CN1319192C (en) * | 2005-05-31 | 2007-05-30 | 中国科学院广州化学研究所 | Method for processing positive pole material of lithium cobalt acid in lithium ion battery |
| CN100436326C (en) * | 2006-10-13 | 2008-11-26 | 福建师范大学 | Method for preparing lithium vanadium oxide for lithium ion cell anode material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530908A (en) * | 2011-12-10 | 2012-07-04 | 桂林理工大学 | Method for preparing silicon doping phosphate manganese lithium lithium-ion battery positive electrode material by sol-gel method |
| CN102769136A (en) * | 2012-07-31 | 2012-11-07 | 山东齐星新材料科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN102769136B (en) * | 2012-07-31 | 2014-08-20 | 山东齐星新材料科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103794775A (en) * | 2014-01-24 | 2014-05-14 | 国家纳米科学中心 | Preparation method of positive electrode material of iron-doped lithium manganate acid lithium ion battery |
| CN103794775B (en) * | 2014-01-24 | 2016-06-22 | 国家纳米科学中心 | A kind of preparation method of Fe2O3 doping manganate lithium ion battery positive electrode |
| CN107946583A (en) * | 2017-12-11 | 2018-04-20 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery LiMn2O4 composite material |
| CN108054363A (en) * | 2017-12-11 | 2018-05-18 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery boron, aluminium adulterated lithium manganate composite material |
| CN113937307A (en) * | 2021-09-10 | 2022-01-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
| CN113937307B (en) * | 2021-09-10 | 2023-03-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
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