CN103779551A - Method for preparing carbon modified lithium ion battery Li4Ti5O12 cathode material in one step - Google Patents

Method for preparing carbon modified lithium ion battery Li4Ti5O12 cathode material in one step Download PDF

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Publication number
CN103779551A
CN103779551A CN201410007679.7A CN201410007679A CN103779551A CN 103779551 A CN103779551 A CN 103779551A CN 201410007679 A CN201410007679 A CN 201410007679A CN 103779551 A CN103779551 A CN 103779551A
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lithium
ion battery
titanium
solution
solubility
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CN201410007679.7A
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Inventor
穆道斌
吴伯荣
杨磊
马云凤
代文慧
赵菲菲
侯雄雄
赵章宏
陶丹
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GAOPING TANGYIXIN NEW ENERGY TECHNOLOGY Co Ltd
Beijing Institute of Technology BIT
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GAOPING TANGYIXIN NEW ENERGY TECHNOLOGY Co Ltd
Beijing Institute of Technology BIT
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Publication of CN103779551A publication Critical patent/CN103779551A/en
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    • 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
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Abstract

The invention relates to a method for preparing a carbon modified lithium ion battery Li4Ti5O12 cathode material in one step, belonging to the technical field of manufacturing processes of chemical electrode materials. According to the method for preparing the carbon modified lithium ion battery Li4Ti5O12 cathode material in one step, a soluble metallic titanium salt and a soluble metallic lithium salt are selected as raw materials, and a carbon source is added to a precursor solution directly, so that carbon is introduced in the process of forming an LTO precursor; the purpose of modifying the rate performance of the Li4Ti5O12 cathode material is achieved through subsequent heat treatment. The carbon modified lithium ion battery Li4Ti5O12 cathode material prepared by using the method has excellent electrochemical performance. Meanwhile, the conductivity of the material is enhanced due to the introduction of the carbon; the carbon modified lithium ion battery Li4Ti5O12 cathode material has high rate charging/discharging performance.

Description

One step is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material
Technical field
The present invention relates to a step and prepare carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, belongs to chemical industry electrode material manufacturing process technology field.
Background technology
In recent years, be the impacts such as traditional petrochemical industry resources such as reply petroleum gas sharply consume, the countries such as the U.S., Japan, China are all actively developing the development and utilization work of clean energy resource, as wind energy and solar energy.And the uncontrollability of wind and solar energy on generating dutation and generated output, and " peak valley effect " in network load, power storage is received much concern as the indispensable link of electrical network " peak load shifting ".And lithium ion battery is as the main candidate's power supply of following energy-accumulating power station, there is feature with low cost, excellent performance, become the main study hotspot in international electrokinetic cell field, be wherein the emphasis of research as the exploitation of the function admirable electrode material that improves one of key factor of performance of lithium ion battery always.
Lithium ion battery has higher requirement as the main candidate's power supply of following energy-accumulating power station to its security performance.At present, the main negative material of applying in lithium ion battery is traditional graphite-like material with carbon element, and material with carbon element, because current potential approaches lithium metal, may cause separating out of lithium metal, thereby causes battery short circuit, causes security incident.In recent years, some non-carbon negative pole materials, due to good cycle performance and higher removal lithium embedded current potential and the more excellent security performance of bringing thus and longer life-span, had become one of focus of lithium ion battery negative material research.Li 4ti 5o 12material is so a kind of long-life negative material, its lattice parameter almost remains unchanged in the process of removal lithium embedded, and can not generate SEI film at material surface, this material essential element titanium is at natural rich content, cost of material is cheap, has good prospect and potentiality as Novel cathode material for lithium ion battery.But due to Li 4ti 5o 12very low (the <10 of the electronic conductivity of material own -13s/cm), cause its poor high rate performance, under high magnification, capacity attenuation is very fast.Recent study personnel are to Li 4ti 5o 12material has carried out a series of study on the modification to improving the high rate performance of material, comprises that 1. employing nanometer beign preparation methods prepare Li 4ti 5o 12material, as hydro thermal method, sol-gal process etc., increases the specific area of material, thereby improves the diffusion rate of lithium ion between electrolyte and electrode.2. introduce highly conductor phase, under solid phase condition, adulterate with highly conductor phases such as carbon, silver, titanium nitrides or be coated Li 4ti 5o 12, utilize highly conductor phase to form conductive network, improve the high rate performance of composite material.3. metal cation doping increases electron hole pair by introduce metal cation in spinel structure in crystal structure, thereby improves the conductivity of material.But these method technological process complexity conventionally, cost is also relatively high.This work has been developed Li by a kind of simple process 4ti 5o 12negative material is also studied its removal lithium embedded performance.
Summary of the invention
The object of the invention is in order to solve existing modification lithium-ion battery Li 4ti 5o 12negative material complex process, the problem that cost is higher, provide an a kind of step to prepare carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material.
The object of the invention is to be achieved through the following technical solutions.
One step is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, concrete steps are as follows:
Step 1, soluble metal titanium salt is dissolved in polar nonaqueous solvent, is labeled as A solution; By soluble in water solubility lithium salts, be labeled as B solution; In B solution, dissolve in solubility carbon source, obtain C solution; In described A solution, solute is 0.1～10:10 with the ratio of solvent; In described solution B, solute lithium salts is 1～5:1～5 with the ratio of the amount of substance of titanium salt; In solution B, the amount of aqueous solvent is 1～10:1～10 with the amount of substance ratio of metal titanium salt; In solution C, in solubility carbon source, in the quality of carbon and metal titanium salt, the mass ratio of titanium is 0.1～5:10;
Step 2, step 1 gained A solution is dropped in C solution, obtain white suspension-turbid liquid;
Step 3, step 2 gained suspension-turbid liquid is placed in to baking oven until bone dry, and pulverizes;
Step 4, the powder that step 3 is obtained are annealed under inert atmosphere, naturally cool to room temperature after annealing, obtain the Li that a step is prepared carbon modification 4ti 5o 12.
The titanium salt of soluble metal described in step 1 is selected from the one in the fluoride of chloride, titanium of nitrate, the titanium of sulfate, the titanium of alkoxide compound, the titanium of lipoid substance, the titanium of titanium; The preferably lipoid substance of titanium;
Polar nonaqueous solvent described in step 1 is the one in ethanol, formamide, acetonitrile, methyl alcohol, propyl alcohol, acetone, dioxane, oxolane, methylethylketone;
The lithium salts of solubility described in step 1 is selected from least one in lithium hydroxide, lithium chloride, isopropyl lithium alkoxide, lithium acetate, lithium nitrate, lithium fluoride, lithium sulfate, lithium phosphate;
The carbon source of solubility described in step 1 is selected from least one in soluble saccharide, solubility lipid, solubility organic acid;
In above-mentioned steps four, annealing temperature is 600 ℃～900 ℃, preferably 800 ℃; Heating rate is 1 ℃～10 ℃/min, preferably 5 ℃/min; Inert gas is argon gas or nitrogen.
Beneficial effect
1, a step of the present invention is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, selecting a kind of soluble metal titanium salt and soluble metal lithium salts is raw material, directly adds carbon source in precursor solution, in formation LTO presoma process, introduces carbon simultaneously, through subsequent heat treatment, reaches modification Li 4ti 5o 12the object of negative material high rate performance.
2, lithium ion battery negative material Li provided by the invention 4ti 5o 12the preparation method of/C; belong to softening method; complete at same liquid phase one-step by controlling slaine and carbon source; the concentration of the soluble metallic salt using in the inventive method can be high or low, thus have advantages of that controllability is strong, simple economy, energy consumption is low, easy to operate and be convenient to accomplish scale production.
3, the prepared lithium ion battery negative material Li of the inventive method 4ti 5o 12/ C, shows excellent chemical property as lithium ion battery negative material.The introducing of carbon has simultaneously strengthened the conductivity of material, shows high rate charge-discharge performance as lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is Li prepared by embodiment 4ti 5o 12the XRD figure of/C negative material;
Fig. 2 is Li prepared by embodiment 4ti 5o 12many multiplying powers cycle graph of/C material.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
Embodiment 1
One step is prepared carbon modification lithium-ion battery Li 4ti 5o 12the process of negative material, concrete steps are:
1) take the butyl titanate (TBT) of 13g, under the state stirring, be dissolved in the absolute alcohol of 20ml continuing, until completely dissolved, under room temperature, continue to stir 30 minutes, be designated as solution A; Separately take the lithium hydroxide of 1.3g and the sucrose of 1.5g, under the state that continues stirring, be dissolved in the deionized water of 13ml, after dissolving completely, under room temperature, continue to stir 30 minutes, be designated as solution B;
2) under the state that continues stirring, with peristaltic pump, A solution is dropwise added in B solution, until A solution is all added dropwise to complete, continuation stirring 2h reacts fully and carries out;
3) the white suspension-turbid liquid of gained is moved in the baking oven of 105 ℃, dry 24h and will obtain solid abrasive and become powder;
4) by gained white powder high-temperature calcination 5h in the tube furnace that is connected with high-purity argon gas, obtain end product;
By the Li obtaining 4ti 5o 12/ C composite negative pole material carries out charging and discharging capacity and high rate performance test: Li after being applied to lithium ion battery negative material 4ti 5o 12/ C negative material and conductive agent, binding agent are mixed and made into electrode slice as work electrode, and lithium metal is to electrode, the LiF of 1mol/L 6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, is assembled into simulated battery.Simulated battery is carried out to charge-discharge test, and voltage range is 1～3V (vs.Li +/ Li), 1C corresponding current density is 175mA/g.
Test result: Li 4ti 5o 12/ C negative material has respectively as shown in Figure 2 the specific capacity of 173.6mAh/g, 160.3mAh/g, 155.4mAh/g, 151.2mAh/g, 147.5mAh/g, 143.3mAh/g under 0.1C, 1C, 2C, 5C, the large multiplying power of 10C, 20C.Show the Li synthesizing by this method 4ti 5o 12/ C negative material has excellent high rate performance.

Claims (6)

1. a step is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: concrete steps are as follows:
Step 1, soluble metal titanium salt is dissolved in polar nonaqueous solvent, is labeled as A solution; By soluble in water solubility lithium salts, be labeled as B solution; In B solution, dissolve in solubility carbon source, obtain C solution; In described A solution, solute is 0.1～10:10 with the ratio of solvent; In described solution B, solute lithium salts is 1～5:1～5 with the ratio of the amount of substance of titanium salt; In solution B, the amount of aqueous solvent is 1～10:1～10 with the amount of substance ratio of metal titanium salt; In solution C, in solubility carbon source, in the quality of carbon and metal titanium salt, the mass ratio of titanium is 0.1～5:10;
Step 2, step 1 gained A solution is dropped in C solution, obtain white suspension-turbid liquid;
Step 3, step 2 gained suspension-turbid liquid is placed in to baking oven until bone dry, and pulverizes;
Step 4, the powder that step 3 is obtained are annealed under inert atmosphere, naturally cool to room temperature after annealing, obtain the Li that a step is prepared carbon modification 4ti 5o 12.
2. a step as claimed in claim 1 is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: the titanium salt of soluble metal described in step 1 is selected from the one in the fluoride of chloride, titanium of nitrate, the titanium of sulfate, the titanium of alkoxide compound, the titanium of lipoid substance, the titanium of titanium; The preferably lipoid substance of titanium.
3. a step as claimed in claim 1 is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: polar nonaqueous solvent described in step 1 is the one in ethanol, formamide, acetonitrile, methyl alcohol, propyl alcohol, acetone, dioxane, oxolane, methylethylketone.
4. a step as claimed in claim 1 is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: the lithium salts of solubility described in step 1 is selected from least one in lithium hydroxide, lithium chloride, isopropyl lithium alkoxide, lithium acetate, lithium nitrate, lithium fluoride, lithium sulfate, lithium phosphate.
5. a step as claimed in claim 1 is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: the carbon source of solubility described in step 1 is selected from least one in soluble saccharide, solubility lipid, solubility organic acid.
6. a step as claimed in claim 1 is prepared carbon modification lithium-ion battery Li 4ti 5o 12the method of negative material, is characterized in that: annealing temperature described in step 4 is 600 ℃～900 ℃, preferably 800 ℃; Heating rate is 1 ℃～10 ℃/min, preferably 5 ℃/min; Inert gas is argon gas or nitrogen.
CN201410007679.7A 2014-01-08 2014-01-08 Method for preparing carbon modified lithium ion battery Li4Ti5O12 cathode material in one step Pending CN103779551A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328918A (en) * 2016-11-04 2017-01-11 中南大学 NiTiO3/C compound material for sodium-ion battery, preparation method and application
CN108306012A (en) * 2018-01-30 2018-07-20 郑州中科新兴产业技术研究院 A kind of anti-flatulence lithium titanate material of high magnification and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101702431A (en) * 2009-10-30 2010-05-05 南京工业大学 Preparation method of lithium titanium negative electrode composite material for lithium ion battery
CN101944591A (en) * 2010-09-14 2011-01-12 耿世达 Lithium titanate anode material for lithium ion batteries and preparation method thereof
CN102285684A (en) * 2011-06-15 2011-12-21 哈尔滨远方新能源汽车动力电池有限责任公司 Preparation method of lithium ion battery negative electrode material Li4Ti5O12

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101702431A (en) * 2009-10-30 2010-05-05 南京工业大学 Preparation method of lithium titanium negative electrode composite material for lithium ion battery
CN101944591A (en) * 2010-09-14 2011-01-12 耿世达 Lithium titanate anode material for lithium ion batteries and preparation method thereof
CN102285684A (en) * 2011-06-15 2011-12-21 哈尔滨远方新能源汽车动力电池有限责任公司 Preparation method of lithium ion battery negative electrode material Li4Ti5O12

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328918A (en) * 2016-11-04 2017-01-11 中南大学 NiTiO3/C compound material for sodium-ion battery, preparation method and application
CN106328918B (en) * 2016-11-04 2019-11-29 中南大学 A kind of NiTiO for sodium-ion battery3/ C composite, preparation and application
CN108306012A (en) * 2018-01-30 2018-07-20 郑州中科新兴产业技术研究院 A kind of anti-flatulence lithium titanate material of high magnification and preparation method thereof

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Application publication date: 20140507