CN101540394B - Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material - Google Patents
Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material Download PDFInfo
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- CN101540394B CN101540394B CN2009100219643A CN200910021964A CN101540394B CN 101540394 B CN101540394 B CN 101540394B CN 2009100219643 A CN2009100219643 A CN 2009100219643A CN 200910021964 A CN200910021964 A CN 200910021964A CN 101540394 B CN101540394 B CN 101540394B
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Abstract
The invention discloses a method for preparing lithium ferrosilicon silicate of a lithium-ion battery cathode material. After the mixture powder of lithium salts, ferrous salts and silicon dioxide is sufficiently ground, the mixture powder is calcined under inert atmosphere so as to obtain the lithium ferrosilicon silicate lithium-ion battery cathode material. The lithium ferrosilicon silicate material is easily and safely prepared with low cost. The lithium ferrosilicon silicate material obtained by the method has the advantages of low cost, good electrochemical performance, environmental protection, and the like and has wide application prospect in the field of the lithium-ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, especially design a kind of new type lithium ion battery positive electrode---the preparation method of ferrosilicon silicate of lithium.
Background technology
Lithium ion battery is since last century, the nineties was come out, owing to its high-energy-density, high power, excellent cycle performance are widely used in all kinds of portable type electronic products field.Along with development of global economy, energy problem is quite outstanding, so the research and development of hybrid vehicle and electric automobile have become global focus, and key technology wherein is exactly the lithium-ion electric pool technology.
Positive electrode is one of critical material of decision lithium ion battery performance, and commercial at present positive electrode is with LiCoO
2Be main, but because LiCoO
2The shortage of resources of middle cobalt costs an arm and a leg, and has toxicity, and environment is had certain pollution, therefore can not adapt to the requirement of large-sized power battery.LiMn
2O
4Though with low cost, cycle performance is poor, fail safe is also relatively poor.Beginning in 1997, many research groups have reported LiMPO
4(M=Fe, Mn, Co, Ni) anode material for lithium-ion batteries finds that this is the up-and-coming positive electrode of a class.Yet, LiFePO
4The electronic conductivity of material and tap density are difficult to improve simultaneously, are difficult to satisfy the needs of the big capacity lithium secondary battery of a new generation.2005, Nyte ' doctor n of Uppsala Univ Sweden synthesized Li first
2FeSiO
4Anode material for lithium-ion batteries obtains comparatively desirable chemical property.Li
2FeSiO
4Belong to rhombic system, space group Pmn2
1, lattice constant is a=6.2661 (5), b=5.3295 (5), c=5.0148 (4)
With Li
3PO
4Low temperature structure similar.At Li
2FeSiO
4In the crystal, Li, Si, Fe form tetrahedral structure with O.Because silicate has that raw material is easy to get and is with low cost etc. tempting, Li
2FeSiO
4Be considered to have the new type lithium ion battery positive electrode of development potentiality.
Summary of the invention
The objective of the invention is to, a kind of preparation method of new type lithium ion battery positive electrode active materials ferrosilicon silicate of lithium is provided, the ferrosilicon silicate of lithium Stability Analysis of Structures of this method preparation, good with the electrolyte compatibility, good electrochemical is arranged.And easy and simple to handle, be easy to control, with low cost.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material is characterized in that, comprises the following steps:
1) in proportion raw material lithium salts, ferrous salt, silicon dioxide and additive are mixed, wherein the mol ratio of Li: Fe: Si is (1.9-2.1): (0.95-1.05): 1, and the addition of additive is 1～30% of a mixture gross mass;
2) mixed uniformly material is put into Equipment for Heating Processing; at flow velocity is heat treated in the inert gas protection of 100～5000ml/min; heating rate is 1 ℃/min～20 ℃/min, when temperature to be heated rises to 300 ℃～450 ℃, keeps; under this temperature, heated 1～30 hour; continue then to heat up, in 700 ℃～900 ℃ scope, heat treatment 10 hours～48 hours; slowly reduce to room temperature then, obtain the ferrous metasilicate lithium material.
Owing in the building-up process of ferrosilicon silicate of lithium, adopted additive among the present invention, these additives are distributed between the material granule by mixing, additive mainly plays two effects: the one, suppress the growth of ferrosilicon silicate of lithium individual particle, and reduce the particle diameter of individual particle.The 2nd, the pyrolytic carbon that the additive pyrolysis forms later on can be coated on particle surface or be present between the particle, thereby improves the electric conductivity between the particle effectively.So in building-up process, add additive can obtain particle diameter little, conduct electricity very well, ferrous metasilicate lithium material that chemical property is good.
The preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material of the present invention has the following advantages:
1, the raw material wide material sources are pollution-free, and cost is low;
2, the preparation technology of material is simple, safe;
3, prepared ferrosilicon silicate of lithium has good microstructure;
4, prepared ferrosilicon silicate of lithium Stability Analysis of Structures, good with the electrolyte compatibility, good electrochemical is arranged.
5, positive electrode involved in the present invention can be widely used in comprising all kinds of mobile electronic products and electric vehicle in all kinds of lithium ion batteries.
Description of drawings
Fig. 1 is the X-ray diffraction style of the prepared ferrosilicon silicate of lithium sample of the embodiment that provides of inventor 1, adopt the Japanese Rigaku D/MAX-2400 of company type X-ray diffractometer, Cu K α target is a radiation source, voltage is 46kV, electric current is 100mA, step-length is 0.02, sweep speed be 10 (°)/min, sweep limits (2 θ) is 3 °～90 °.
Fig. 2 is the ESEM picture of the prepared ferrosilicon silicate of lithium sample of the embodiment that provides of inventor 1, utilizes the JSM-6700F of NEC company type field emission scanning electron microscope (FESEM) to take.
Fig. 3 is the first charge-discharge curve chart by the prepared ferrous silicate lithium anode material of embodiment 1.
Fig. 4 is the cycle life curve chart by the prepared ferrous silicate lithium anode material of embodiment 1.
Fig. 5 is the first charge-discharge curve chart by the prepared ferrous silicate lithium anode material of embodiment 2.
Fig. 6 is the first charge-discharge curve chart by the prepared ferrous silicate lithium anode material of embodiment 3.
The embodiment that provides below in conjunction with accompanying drawing and inventor is described in further detail the present invention.
Embodiment
The present invention relates to the preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material, its step is as follows:
1, lithium salts, ferrous salt, silicon dioxide and additive are mixed in proportion that (mixed process can be carried out, as mixing in inclined mill, cone-type mixer, the three-dimensional mixer 1～24 hour in the mixing apparatus of routine; Also available wet chemical method mixes as sol-gel process, spray drying process), wherein, the mol ratio of Li: Fe: Si is (1.9-2.1): (0.95-1.05): the addition of 1 additive is 1～30% of a mixture gross mass;
Above-mentioned additive can be the organic compound that can be decomposed into conductive carbon class material after carbon black, graphite or the pyrolysis;
2; mixed uniformly raw material are put into Equipment for Heating Processing, and (any Equipment for Heating Processing that can evenly add thermal reaction mixture under atmosphere protection all can be used; as the tubular type atmosphere furnace; rotation atmosphere furnace or atmosphere protection continuous tunnel furnace; box type furnace etc.); at flow velocity is heat treated in the inert gas shielding of 100～5000ml/min; heating rate is 1～20 ℃/min; when temperature to be heated rises to 300～450 ℃; keep temperature-resistant; under this temperature, heated 1～30 hour; continue then to heat up; in 700～900 ℃ scope; room temperature is slowly reduced in heat treatment 10～48 hours then, just can obtain the ferrous metasilicate lithium material.
Wherein, the lithium salts, the ferrous salt that prepare above-mentioned positive electrode active materials all do not have particular restriction, can adopt commercially available prod or product well known in the art, as lithium salts can select lithium metasilicate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate, lithium phosphate etc. wherein any, perhaps said mixture etc. can.Ferrous salt can select ferrous oxalate, ferrous acetate, frerrous chloride, ferrous phosphate etc. wherein any, perhaps said mixture etc. can.
Additive can be selected from carbon black, graphite, sucrose, citric acid, glucose, polyvinyl alcohol, soluble starch, phenolic resins, furfural resin, poly-one or more mixtures to benzene, benzene naphthalene dicarboxylic copolymer, benzene anthracene bipolymer, the luxuriant and rich with fragrance bipolymer of benzene, benzene naphthalene terpolymer, benzene naphthalene anthracene terpolymer etc.
Described inert gas such as nitrogen, argon gas or its mist.
In order to be illustrated more clearly in the present invention, the inventor provides following embodiment, need to prove, these embodiment are some more excellent examples, the invention is not restricted to these embodiment.
Embodiment 1:
With 2.7g lithium metasilicate, 5.4g ferrous oxalate, 2g sucrose mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 200r/min.With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours; then with the pressure compressing tablet of 10MPa; under the argon gas atmosphere protection of 1L/min; speed with 10 ℃/min rises to 400 ℃; insulation is 2 hours under this temperature; speed with 10 ℃/min rises to 800 ℃ then, is incubated 10h under this temperature, is cooled to room temperature then and has both obtained the ferrosilicon silicate of lithium sample.
Fig. 1 is the XRD figure spectrum of gained ferrosilicon silicate of lithium, and most diffraction maximum can be corresponding with the characteristic peak of ferrosilicon silicate of lithium among the figure, also has a spot of impurity simultaneously.Fig. 2 is the stereoscan photograph of gained ferrosilicon silicate of lithium, the granularity of synthetic material between 0.5-3 μ m, subsphaeroidal pattern, distribution uniform.
Embodiment 1 gained sample carries out electrochemical property test as follows: ferrosilicon silicate of lithium sample powder, conductive black and PVDF (polyvinylidene fluoride) are pressed 80: 10: 10 mixed of mass ratio, add an amount of organic solvent NMP (N-methyl pyrrolidone), be applied on the aluminium foil 120 ℃ of dry 12h in vacuum drying chamber after fully stirring into even pastel.Cut-off directly is that the small pieces of 16mm are positive pole, and metal lithium sheet is a negative pole, and the Celgard2400 microporous polypropylene membrane is a barrier film, to be dissolved in the 1molL that volume ratio is EC (ethylene carbonate)/DMC (1, the 2-dimethyl carbonate) of 1: 1
-1LiPF
6Be electrolyte, in being full of the glove box of argon gas, be assembled into CR2032 type button cell.Button cell is placed its chemical property of test on the CT2001A type battery test system.Charge-discharge magnification is C/10, and voltage range is 1.5V-4.8V.Fig. 3 is this material first charge-discharge curve, and as seen from the figure, the charging capacity of the material that is synthesized reaches 242mAh/g, and reversible capacity is 137mAh/g, and Fig. 4 provides 10 cyclic curve figure of this material, and as seen the cycle performance of this material is good.
Embodiment 2:
With 2.85g lithium carbonate, 2.3g silicon dioxide, 5.4g ferrous oxalate and 2g sucrose mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min.With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours; then with the pressure compressing tablet of 10MPa; under the argon gas atmosphere protection of 2L/min; speed with 10 ℃/min rises to 400 ℃; insulation is 2 hours under this temperature; speed with 20 ℃/min rises to 850 ℃ then, is incubated 15h under this temperature, is cooled to room temperature then and has both obtained the ferrosilicon silicate of lithium sample.Test its chemical property according to the method for embodiment 1, as shown in Figure 5, its first circulating and reversible capacity is 142mAh/g.
Embodiment 3:
With 1.85g lithium hydroxide, 2.3g silicon dioxide, 5.4g ferrous oxalate and 1.5g citric acid mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min.With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours; then with the pressure compressing tablet of 10MPa; under the argon gas atmosphere protection of 1.5L/min; speed with 5 ℃/min rises to 400 ℃; insulation is 1 hour under this temperature; speed with 10 ℃/min rises to 750 ℃ then, is incubated 15h under this temperature, is cooled to room temperature then and has both obtained the ferrosilicon silicate of lithium sample.Test its chemical property according to the method for embodiment 1, as shown in Figure 6, its first circulating and reversible capacity is 118mAh/g.
Embodiment 4:
Different is for present embodiment and embodiment 1, only additive is changed into the 0.5g conductive black, and all the other are with embodiment 1, and the first circulating and reversible capacity of gained positive electrode is 138mAh/g.
Embodiment 5:
Different is for present embodiment and embodiment 2, only additive is changed into the 1g citric acid, and all the other are with embodiment 2, and the first circulating and reversible capacity of gained positive electrode is 125mAh/g.
Embodiment 6:
Different is for present embodiment and embodiment 3, only additive is changed into the 1.8g soluble starch, and all the other are with embodiment 3, and the first circulating and reversible capacity of gained positive electrode is 128mAh/g.
Claims (1)
1. the preparation method of a lithium ferrosilicon silicate of lithium-ion battery cathode material is characterized in that, comprises the following steps:
With 2.7g lithium metasilicate, 5.4g ferrous oxalate, 2g sucrose mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 200r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours, then with the pressure compressing tablet of 10MPa, under the argon gas atmosphere protection of 1L/min, speed with 10 ℃/min rises to 400 ℃, insulation is 2 hours under this temperature, and the speed with 10 ℃/min rises to 800 ℃ then, is incubated 10h under this temperature, be cooled to room temperature at last and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 137mAh/g;
Perhaps with 2.85g lithium carbonate, 2.3g silicon dioxide, 5.4g ferrous oxalate and 2g sucrose mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours, then with the pressure compressing tablet of 10MPa, under the argon gas atmosphere protection of 2L/min, speed with 10 ℃/min rises to 400 ℃, insulation is 2 hours under this temperature, and the speed with 20 ℃/min rises to 850 ℃ then, is incubated 15h under this temperature, be cooled to room temperature at last and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 142mAh/g;
Perhaps with 1.85g lithium hydroxide, 2.3g silicon dioxide, 5.4g ferrous oxalate and 1.5g citric acid mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours, then with the pressure compressing tablet of 10MPa, under the argon gas atmosphere protection of 1.5L/min, speed with 5 ℃/min rises to 400 ℃, insulation is 1 hour under this temperature, and the speed with 10 ℃/min rises to 750 ℃ then, is incubated 15h under this temperature, be cooled to room temperature then and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 118mAh/g;
Perhaps with 2.7g lithium metasilicate, 5.4g ferrous oxalate, 0.5g conductive black mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 200r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours, then with the pressure compressing tablet of 10MPa, under the argon gas atmosphere protection of 1L/min, speed with 10 ℃ of min rises to 400 ℃, insulation is 2 hours under this temperature, and the speed with 10 ℃/min rises to 800 ℃ then, is incubated 10h under this temperature, be cooled to room temperature then and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 138mAh/g;
Perhaps with 2.85g lithium carbonate, 2.3g silicon dioxide, 5.4g ferrous oxalate and 1g citric acid mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours, then with the pressure compressing tablet of 10MPa, under the argon gas atmosphere protection of 2L/min, speed with 10 ℃/min rises to 400 ℃, insulation is 2 hours under this temperature, and the speed with 20 ℃/min rises to 850 ℃ then, is incubated 15h under this temperature, be cooled to room temperature at last and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 125mAh/g;
Perhaps with 1.85g lithium hydroxide, 2.3g silicon dioxide, 5.4g ferrous oxalate and 1.8g soluble starch mixing and ball milling 24 hours under ethanol medium, use equipment to be planetary ball mill, the autobiography rotating speed is 250r/min; With the mixed-powder of abundant mixed grinding 60 ℃ of vacuumizes 24 hours; then with the pressure compressing tablet of 10MPa; under the argon gas atmosphere protection of 1.5L/min; speed with 5 ℃/min rises to 400 ℃; insulation is 1 hour under this temperature, and the speed with 10 ℃/min rises to 750 ℃ then, is incubated 15h under this temperature; be cooled to room temperature then and both obtained the ferrosilicon silicate of lithium sample, first circulating and reversible capacity is 128mAh/g.
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| CN101920971B (en) * | 2010-06-28 | 2011-11-16 | 宁波大学 | Preparation method of silicate positive electrode material for lithium ion battery |
| CN102958836A (en) * | 2010-06-30 | 2013-03-06 | 霍加纳斯股份有限公司 | Lithium iron silicate cathode material and production thereof |
| CN101944594B (en) * | 2010-09-14 | 2013-01-09 | 耿世达 | Lithium ferrous silicate anode material for high-performance lithium ion battery and preparation method thereof |
| CN101982410B (en) * | 2010-10-15 | 2012-06-06 | 福建师范大学 | Preparation method of rare earth compound doped lithium ferrous silicate cathode material |
| WO2012110931A1 (en) * | 2011-02-14 | 2012-08-23 | Basf Se | Electrode materials and process for producing them |
| CN102315438A (en) * | 2011-05-23 | 2012-01-11 | 江苏正彤电子科技有限公司 | A porous C/Li2MSiO4/C (M=Fe, mn, co) composite anode material and its preparation method |
| EP2535969A1 (en) * | 2011-06-14 | 2012-12-19 | Höganäs AB | Novel method and product |
| CN102509776B (en) * | 2011-10-19 | 2014-01-29 | 兰州理工大学 | Method for preparing doped ferrous-lithium metasilicate anode material from micro silicon powder |
| CN102664262A (en) * | 2012-05-18 | 2012-09-12 | 哈尔滨工业大学 | Method for preparing lithium ferrous silicate or carbon ferrous silicate cathode material for lithium ion battery |
| CN102709561A (en) * | 2012-06-19 | 2012-10-03 | 中国科学院福建物质结构研究所 | Preparation method of carbon nano-Li2FeSiO4 composite cathode material |
| CN102969503B (en) * | 2012-12-04 | 2015-08-12 | 奇瑞汽车股份有限公司 | Composite material of composition silicate and carbon and preparation method thereof, lithium ion battery containing this material |
| CN104362318B (en) * | 2014-11-10 | 2016-10-05 | 湖南文理学院 | A kind of method of the lithium ferrosilicon silicate/carbon composite cathode material preparing micropore spherical structure |
| CN108807988B (en) * | 2018-07-25 | 2021-04-20 | 四川理工学院 | Preparation method of spherical lithium ferrous silicate cathode material for lithium ion battery |
| CN109638274B (en) * | 2018-12-14 | 2022-03-11 | 廊坊绿色工业技术服务中心 | Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof |
| CN111048766A (en) * | 2019-12-27 | 2020-04-21 | 惠州亿纬锂能股份有限公司 | Lithium iron silicate/carbon cathode material and preparation method and application thereof |
| CN111647863B (en) * | 2020-07-02 | 2022-03-25 | 河北大学 | Li2FexSiO4Preparation method and application of positive electrode film |
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