CN104241626A - Sol-gel preparation method of lithium vanadate negative electrode material of lithium ion battery - Google Patents
Sol-gel preparation method of lithium vanadate negative electrode material of lithium ion battery Download PDFInfo
- Publication number
- CN104241626A CN104241626A CN201310238638.4A CN201310238638A CN104241626A CN 104241626 A CN104241626 A CN 104241626A CN 201310238638 A CN201310238638 A CN 201310238638A CN 104241626 A CN104241626 A CN 104241626A
- Authority
- CN
- China
- Prior art keywords
- lithium
- carbon
- ion battery
- lithium ion
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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 sol-gel preparation method of a lithium vanadate negative electrode material of a lithium ion battery. The sol-gel preparation method comprises the following steps: sequentially adding a precursor containing a vanadium compound and a precursor containing a lithium compound into water, and stirring fully; then adding a water soluble carbon material which is acted as a chelate and a carbon source, stirring the water solution until dry gel is formed, carrying out vacuum drying until the water content is dried completely, putting a gel body into a porcelain boat, pretreating in the reducing atmosphere or the inert atmosphere, and carrying out sintering reaction in the inert atmosphere or the reducing atmosphere so as to obtain the material. According to the method, the technology is simple, the operation is easy, and moreover, the structure of lithium vanadate and the valence state of vanadium cannot be changed by the existence of the carbon material and the reducing atmosphere. The carbon-coated lithium vanadate material synthesized by the method, which acts as the negative electrode material of the lithium ion battery, has excellent performance and low lithium intercalation potential, and is expected to be as the negative electrode material of the next generation of lithium ion batteries. The synthesis method is suitable for producing the negative electrode material of the high-performance lithium ion battery, namely lithium vanadate.
Description
Technical field
The present invention relates to a kind of process for preparing sol-gel of lithium ion battery negative material.By the lithium vanadate negative material electrochemical performance of the method synthesis, intercalation potential low (0.1 ~ 1V), promises to be lithium ion battery negative material of future generation.
Background technology
The operating voltage of lithium ion battery is higher, and the commercial operating voltage using cobalt acid lithium as the general monomer lithium ion battery of positive electrode is for 3.6V, is 3 times of general MH-Ni, Cd-Ni battery operating voltage; Simultaneously it have that volume is little, quality light, quality with volumetric specific energy is high, power output comparatively greatly, have extended cycle life, the advantage such as fast charging and discharging, self-discharge rate are low, memory-less effect, be widely used in various portable equipment, digital product and hybrid vehicle.
Since Sony Corporation releases commercial lithium ion battery 1991, just start the research boom of lithium ion battery associated materials.Lithium ion battery itself is a complicated physical-chemical system, wherein uses multiple material, and main has positive electrode, negative material, collector, barrier film and electrolyte etc.Along with the function of various multimedia portable product becomes more diverse, it also promotes day by day to the performance requirement of battery, proposes higher requirement to the quality of battery and volume and capacity ratio, output voltage, stability, fast charging and discharging ability, cycle life etc.Particularly progressively come into the market based on the electric automobile (EV) of lithium ion battery or hybrid vehicle (HEV), the lithium ion battery of high-output power, high-energy-density, high security becomes people and pays close attention to and the emphasis of research.
1980, Mizushima group proposed and uses stratiform LiCoO
2as the idea of positive electrode, provided possibility for using graphite cathode afterwards.Nineteen ninety, Sony Corporation takes the lead in commercially releasing with LiCoO
2for positive electrode, graphite are as the lithium ion battery of negative material, nominal voltage is 3.6V, and capacity is about 130mAh/g.They have reliable performance and long cycle life, are still widely used at present in the various portable electronic products such as mobile phone, notebook computer, video camera, panel computer.Two during the last ten years, and lamellar graphite is always in occupation of the leading position of commercial Li-ion battery negative material.But, huge potential safety hazard is had: due to its intercalation potential low (~ 0.1V) using graphite as negative pole, easily cause lithium metal to form Li dendrite in the deposition of negative terminal surface in lithium ion battery charge and discharge process, pierce through barrier film and cause short circuit finally to cause battery catches fire or blast.The performance of this point on high-power battery is particularly outstanding, becomes the key of restriction lithium ion battery further application and development in electric automobile (EV) or hybrid vehicle (HEV).Therefore, battery circle is striving to find the negative material that can substitute graphite always.
Do the problems such as the fail safe of negative pole to solve graphite, battery circle has done large quantifier elimination.Find the key that the new more high power capacity graphite substitution material that lithium ion deintercalation voltage is corrected a little simultaneously becomes people's research.
Lithium titanate [the Li of spinel structure
4ti
5o
12] be considered to the different embedding off line produced compounds of best performance except graphite.This material requires higher high power battery is applied because its structural change in the embedding de-process of lithium ion is minimum and reversibility is thus very possible very well in security performance.But, higher lithium ion deintercalation current potential (~ 1.5V) and limited specific capacity (~ 150 mAh g
-1) fundamentally limit further developing of lithium titanate.
Lithium vanadate [Li
3vO
4although] be widely studied as a kind of good Lithium Ionic Conducting Materials, due to low electric conductivity, this material is never found as the effect of lithium ion battery negative material.With LiFePO
4the electrode material poor etc. numerous electrical conductance is similar, and the approach solving lithium vanadate low conductivity has: the intrinsic conductivity 1) being changed material by doping; 2) its conductivity is improved by Surface coating conductive material; 3) reduce material grains size by improving technique and improve its conductivity.Wherein, sol-gal process synthetic material minimizing crystallite dimension and material with carbon-coated surface is adopted to be two kinds of the most frequently used and effective approach.But, at present the general high temperature solid-state method under air atmosphere or sol-gel process are also confined to the synthetic method of this material, but due to lithium vanadate intrinsic conductivity very low, the conductivity of these two kinds of synthetic methods to this material does not have clear improvement.The present invention (comprises air under first adopting different atmosphere, inert atmosphere and reducing atmosphere) sol-gel process and synthesize lithium vanadate, find that the existence of material with carbon element and reducing atmosphere can not make the valence state of the structure of lithium vanadate and vanadium (+5 valency) change, this provides foundation with regard to the lithium vanadate for being had both high ion conductivity and electronic conductivity by the coated synthesis of carbon simultaneously.Content of the present invention shows, the material synthesized by the method, the coated lithium vanadate [Li of carbon of the sol-gel process synthesis particularly under inert atmosphere or reducing atmosphere
3vO
4] material, as lithium ion battery negative material excellent performance, intercalation potential low (0.1 ~ 1V), specific capacity is high, and (first discharge specific capacity reaches 650 mAh g
-1), promise to be lithium ion battery negative material of future generation.This synthetic method is applicable to produce high performance lithium ionic cell cathode material lithium vanadate.
Summary of the invention
The object of the invention is sol-gel process, find a kind of method preparing high-performance vanadic acid lithium titanate cathode material.Meanwhile, for the shortcoming that lithium vanadate electronic conductivity is low, adopt sol-gel process under inert atmosphere or reducing atmosphere, utilize relatively cheap water-soluble carbon material to carry out material with carbon-coated surface to it, substantially increase its conductivity and chemical property.The present invention have found that a kind of technique is simple, abundant raw material source, be suitable for the method for suitability for industrialized production.The object of the invention is to realize by the following technical solutions:
(1) presoma of vanadium-containing compound and lithium-containing compound be added to the water successively according to stoichiometric number ratio and fully stir, forming the aqueous solution; Wherein, calculate according to stoichiometry, the mol ratio of lithium and v element is 3:1; Described vanadium-containing compound is the oxide of vanadic salts or vanadium, and described lithium-containing compound is the alkali compounds of lithium salts or lithium.
(2) add at the formed aqueous solution that water-soluble carbon material is double does chelate and carbon source, by little of formation xerogel for the lower stirring 2 ~ 10 at 50 ~ 100 DEG C of temperature of this aqueous solution;
(3) the colloid vacuumize at 60 ~ 120 DEG C will obtained, puts into tube furnace, and 250 ~ 450 DEG C of preliminary treatment 2 ~ 12 hours under reducing atmosphere or inert atmosphere, obtain dusty material after cooling naturally;
(4), after dusty material grinding step (3) obtained, in tube furnace, be again heated to 500 ~ 900 DEG C, under reducing atmosphere or inert atmosphere, process 2 ~ 12 hours, naturally obtain the coated lithium vanadate negative material of carbon after cooling;
Lithium-containing compound described in above-mentioned preparation comprises lithium carbonate (Li
2cO
3), lithium acetate (CH
3cOOLi), lithium hydroxide (LiOH), lithium nitrate (LiNO
3) in one.
Vanadium-containing compound described in above-mentioned preparation comprises V
2o
5, VO
2, V
2o
3or NH
4vO
3in one.
Reducing atmosphere described in above-mentioned preparation comprises Ar/H
2gaseous mixture, N
2/ H
2gaseous mixture, hydrogen, carbon monoxide or ammonia; Described inert atmosphere comprises Ar, N
2, CO
2or He gas.
Water-soluble carbon material described in above-mentioned preparation be that be made up of carbon, hydrogen, oxygen three kinds of elements, water-soluble, carbon compound can be produced at high temperature lower than cracking under the anaerobic state of reaction temperature, the addition of water-soluble carbon material meets the amount that its cracking to produce carbon and accounts for 1 ~ 20% of the coated lithium vanadate negative material gross mass of final carbon.
Water-soluble carbon material described in above-mentioned preparation is sucrose, glucose or citric acid.
The present invention is directed to the low shortcoming being difficult to be used as commercial lithium-ion batteries negative material of lithium vanadate electronic conductivity, adopt sol-gel process under inert atmosphere or reducing atmosphere, relatively cheap water-soluble carbon is utilized to carry out material with carbon-coated surface to it, reduce the crystallite dimension of material simultaneously and improve conductivity, substantially improve its chemical property, find that a kind of technique is simple, abundant raw material source, be suitable for producing the method for high performance lithium ionic cell cathode material lithium vanadate.Generally speaking, the present invention has following outstanding feature:
(1) the present invention adopts sol-gel process to synthesize lithium vanadate, preliminary treatment and sintering process both can be carried out in an inert atmosphere, also can carry out in reducing atmosphere, the existence of material with carbon element and reducing atmosphere can not make the valence state of the structure of lithium vanadate and vanadium (+5 valency) change simultaneously.This just provides foundation for preparing the coated lithium vanadate of carbon under inert atmosphere or reducing atmosphere to improve its conductivity.
(2) adopt the method for collosol and gel of liquid phase to carry out mixed material, make reaction raw materials in liquid phase environment, reach Homogeneous phase mixing on atomic level, thus avoid the generation of impurity phase.
(3) reduce reaction temperature, Reaction time shorten, product grain is even, and specific area is large, and performance is higher, has the cycle performance that higher reversible capacity is become reconciled.Meanwhile, reduce production cost, make course of reaction be convenient to control.
(4) under liquid phase state, add carbon encapsulated material, make covered effect evenly complete, thus improve product property.
(5) the present invention synthesis the coated lithium vanadate negative material of carbon and metal lithium sheet form test cell, with 0.18C rate charge-discharge, when charging voltage is 0.1-2.5V, reach 670mAh/g and 515mAh/g. respectively with second time specific discharge capacity first
accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the embodiment of the present invention 1 and embodiment 2, and wherein (a) curve is the X ray diffracting spectrum of inventive embodiments 1, and (b) curve is the X ray diffracting spectrum of embodiment 2.
Fig. 2 is the scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 processes 6 hours at 650 DEG C.
Fig. 3 be the embodiment of the present invention 1 0.1-2.5V first with second time charging and discharging curve, wherein a is initial charge curve, and b is discharge curve first, and c is second time charging curve, and d is second time discharge curve.
Fig. 4 is the cycle performance curve of the embodiment of the present invention 1 in 0.1-2.5V voltage range under different current density.
Fig. 5 be the embodiment of the present invention 2 0.1-2.8V first with second time charging and discharging curve, wherein a is initial charge curve, and b is discharge curve first, and c is second time charging curve, and d is second time discharge curve.
Fig. 6 is the cycle performance curve of the embodiment of the present invention 2 at 0.1-2.8V.
Fig. 7 is the X ray diffracting spectrum of the embodiment of the present invention 3 and embodiment 4, and wherein (a) curve is the X ray diffracting spectrum of inventive embodiments 3, and (b) curve is the X ray diffracting spectrum of embodiment 4.
Fig. 8 be the embodiment of the present invention 3 0.1-2.8V first with second time charging and discharging curve, wherein a is initial charge curve, and b is discharge curve first, and c is second time charging curve, and d is second time discharge curve.
Fig. 9 be the embodiment of the present invention 4 0.1-2.5V first with second time charging and discharging curve, wherein a is initial charge curve, and b is discharge curve first, and c is second time charging curve, and d is second time discharge curve.
Embodiment
In order to understand the present invention better, below in conjunction with embodiment and accompanying drawing, the invention will be further described, but invent claimed scope and be not limited to the scope that embodiment represents.
embodiment 1
3.091g lithium acetate was dissolved in 60mL distilled water, under the condition of magnetic agitation, added 0.918g vanadium pentoxide powder and 2.112g citric acid successively, and made it finally to form light blue solution.Wherein the amount of citric acid in amount of substance than citric acid: the ratio of vanadium=1:1 adds, other materials then stoichiometrically Li:V=3:1 add.The solution be mixed to form is placed in 80 DEG C of thermostat water baths by moisture evaporate to dryness gradually under the condition of magnetic agitation, after forming xerogel, puts it into 80 DEG C of continuation in vacuum drying chamber and moisture is dried completely.Then the sample after oven dry is loaded in ceramic crucible and put into quartz tube furnace at 30%H
2+ 70%Ar(Volume fraction) lower 400 DEG C of pre-burnings of reducing atmosphere 4 hours, carefully grinding after taking out after cooling, then 650 DEG C of process 6 hours under identical atmospheric condition, obtain the coated lithium vanadate negative material of carbon after naturally cooling.The X-ray diffractogram of product is shown in (a) curve in Fig. 1, and as seen from the figure, the lithium vanadate negative material of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high.The scanning electron microscopic picture of this product is shown in Fig. 2, can see that the granular size of product is at about 100 nm, and the coated and even grade particles of carbon can improve specific area and the conductivity of material, thus makes product have circulation and high rate performance preferably.Lithium vanadate negative material prepared by this sol-gel process is in 0.1-2.5V voltage range, and multiplying power is 0.18C(80 mA/g) first with second time specific discharge capacity respectively up to 670 mAh/g and 515 mAh/g, charging and discharging curve is as shown in Figure 3.Fig. 4 is shown in the charge/discharge capacity performance test of this material under different current density, as seen from Figure 4, charging/discharging voltage is 0.1-2.5V, and current density is respectively the charging and discharging capacity of this material under 80 mA/g, 300 mA/g, 500 mA/g, 700 mA/g and 1000 mA/g and substantially remains on 300 more than mAh/g; When current density gets back to 300 mA/g again, the charging and discharging capacity of this material substantially can get back to before level, be about 374 mAh/g, indicate the good cycle performance of this material and high rate performance.
embodiment 2
Be dissolved in by 1.131g lithium carbonate in 60mL distilled water, and added 0.918g vanadium pentoxide powder and 2.112g citric acid under the condition of magnetic agitation successively, the generation with a large amount of bubble finally forms blue solution.Wherein the amount of citric acid in amount of substance than citric acid: the ratio of vanadium=1:1 adds, other materials then stoichiometrically Li:V=3:1 add.The solution be mixed to form is placed in 75 DEG C of thermostat water baths by moisture evaporate to dryness gradually under the condition of magnetic agitation, after forming xerogel, is put 90 DEG C of continuation in vacuum drying chamber and moisture is dried completely.Then the sample after drying is loaded in ceramic crucible and put into quartz tube furnace 350 DEG C of pre-burnings 4 hours in a nitrogen atmosphere, carefully grinding after taking out after cooling, again under identical atmospheric condition 800 DEG C process 6 hours, naturally cool after obtain the coated lithium vanadate negative material of carbon.The X-ray diffractogram of product is shown in (b) curve in Fig. 1, and as seen from the figure, the lithium vanadate negative material of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high.This lithium vanadate negative material in 0.1-2.8V voltage range, current density be 200 mA/g first with second time charging and discharging curve as shown in Figure 5.As shown in Figure 6, the lithium vanadate negative material utilizing the method to synthesize as can be seen from Figure has excellent cycle performance to cycle performance, and after 50 circulations, specific discharge capacity is 353.1 mAh/g, is 83% of the second circulation specific discharge capacity.
embodiment 3
1.259g lithium hydroxide was dissolved in 60mL distilled water, under the condition of magnetic agitation, added 0.918g vanadium pentoxide powder and 1.820g glucose successively, and made it finally to form blue solution.Wherein the amount of glucose in amount of substance than glucose: the ratio of vanadium=1:1 adds, other materials then stoichiometrically Li:V=3:1 add.The solution be mixed to form is placed in 70 DEG C of thermostat water baths by moisture evaporate to dryness gradually under the condition of magnetic agitation, after forming xerogel, puts it into 90 DEG C of continuation in vacuum drying chamber and moisture is dried completely.Then the sample after drying is loaded in ceramic crucible and put into quartz tube furnace 350 DEG C of pre-burnings 4 hours in a nitrogen atmosphere, carefully grinding after taking out after cooling, again under identical atmospheric condition 500 DEG C process 6 hours, naturally cool after obtain the coated lithium vanadate negative material of carbon.The X-ray diffractogram of product is shown in (a) curve in Fig. 7, and as seen from the figure, the lithium vanadate negative material of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high.This lithium vanadate negative material in 0.1-2.8V voltage range, current density be 80 mA/g first with second time charging and discharging curve as shown in Figure 8.
embodiment 4
2.089g lithium nitrate was dissolved in 60mL distilled water, under the condition of magnetic agitation, added 1.182g ammonium metavanadate and 1.728g sucrose successively, and made it finally to form blue solution.Wherein the amount of sucrose in amount of substance than sucrose: the ratio of vanadium=1:2 adds, other materials then stoichiometrically Li:V=3:1 add.The solution be mixed to form is placed in 80 DEG C of thermostat water baths by moisture evaporate to dryness gradually under the condition of magnetic agitation, after forming xerogel, puts it into 80 DEG C of continuation in vacuum drying chamber and moisture is dried completely.Then the sample after drying is loaded in ceramic crucible and put into quartz tube furnace 350 DEG C of pre-burnings 4 hours under high-purity Ar atmosphere, carefully grinding after taking out after cooling, again under identical atmospheric condition 800 DEG C process 6 hours, naturally cool after obtain the coated lithium vanadate negative material of carbon.The X-ray diffractogram of product is shown in (b) curve in Fig. 7, and as seen from the figure, the lithium vanadate negative material of the pure phase that utilized the method to synthesize, there is not impurity peaks in spectrogram, product purity is high.This lithium vanadate negative material in 0.1-2.5V voltage range, current density be 80 mA/g first with second time charging and discharging curve as shown in Figure 9.
As can be seen from the above-described embodiment, when adopting the method for sol-gel under inert atmosphere or reducing atmosphere to prepare lithium vanadate negative material, water-soluble carbon material is added under liquid phase state, make covered effect evenly complete, effectively can reduce the reunion of crystal grain, make production die less, specific area increases, thus improves the ion diffusion rates of product; Carbon is to the coated electronic conductivity that improve product of lithium vanadate simultaneously, therefore, the lithium vanadate using the carbon that prepared by the method for sol-gel under inert atmosphere or reducing atmosphere coated has higher specific discharge capacity than the pure phase lithium vanadate using simple high temperature solid-state method to synthesize.
Claims (6)
1. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material, is characterized in that comprising the steps:
(1) presoma of vanadium-containing compound and lithium-containing compound be added to the water successively according to stoichiometric number ratio and fully stir, forming the aqueous solution; Wherein, calculate according to stoichiometry, the mol ratio of lithium and v element is 3:1; Described vanadium-containing compound is the oxide of vanadic salts or vanadium, and described lithium-containing compound is the alkali compounds of lithium salts or lithium;
(2) add at the formed aqueous solution that water-soluble carbon material is double does chelate and carbon source, by little of formation xerogel for the lower stirring 2 ~ 10 at 50 ~ 100 DEG C of temperature of this aqueous solution;
(3) the colloid vacuumize at 60 ~ 120 DEG C will obtained, puts into tube furnace, and 250 ~ 450 DEG C of preliminary treatment 2 ~ 12 hours under reducing atmosphere or inert atmosphere, obtain dusty material after cooling naturally;
(4), after dusty material grinding step (3) obtained, in tube furnace, be again heated to 500 ~ 900 DEG C, under reducing atmosphere or inert atmosphere, process 2 ~ 12 hours, naturally obtain the coated lithium vanadate negative material of carbon after cooling.
2. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material according to claim 1, is characterized in that: the lithium-containing compound described in step (1) comprises lithium carbonate (Li
2cO
3), lithium acetate (CH
3cOOLi), lithium hydroxide (LiOH), lithium nitrate (LiNO
3) in one.
3. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material according to claim 1, is characterized in that: the vanadium-containing compound described in step (1) comprises V
2o
5, VO
2, V
2o
3or NH
4vO
3in one.
4. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material according to claim 1, is characterized in that: step (3), the reducing atmosphere described in (4) comprise Ar/H
2gaseous mixture, N
2/ H
2gaseous mixture, hydrogen, carbon monoxide or ammonia; Described inert atmosphere comprises Ar, N
2, CO
2or He gas.
5. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material according to claim 1, it is characterized in that: the water-soluble carbon material described in step (2) be that be made up of carbon, hydrogen, oxygen three kinds of elements, water-soluble, carbon compound can be produced at high temperature lower than cracking under the anaerobic state of reaction temperature, the addition of water-soluble carbon material meets the amount that its cracking to produce carbon and accounts for 1 ~ 20% of the coated lithium vanadate negative material gross mass of final carbon.
6. the process for preparing sol-gel of lithium ion battery lithium vanadate negative material according to claim 5, is characterized in that: described water-soluble carbon material is sucrose, glucose or citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310238638.4A CN104241626B (en) | 2013-06-17 | 2013-06-17 | The process for preparing sol-gel of lithium ion battery lithium vanadate negative material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310238638.4A CN104241626B (en) | 2013-06-17 | 2013-06-17 | The process for preparing sol-gel of lithium ion battery lithium vanadate negative material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104241626A true CN104241626A (en) | 2014-12-24 |
| CN104241626B CN104241626B (en) | 2016-10-05 |
Family
ID=52229306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310238638.4A Active CN104241626B (en) | 2013-06-17 | 2013-06-17 | The process for preparing sol-gel of lithium ion battery lithium vanadate negative material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104241626B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681784A (en) * | 2015-02-10 | 2015-06-03 | 华中科技大学 | Lithium vanadate anode material, anode, battery and anode material preparation method |
| CN104934577A (en) * | 2015-05-15 | 2015-09-23 | 武汉理工大学 | Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material |
| CN105529450A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | Preparation method for lithium ion battery cathode material fluorine-doped lithium vanadate with circulatory stability |
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery |
| CN106058217A (en) * | 2016-08-11 | 2016-10-26 | 复旦大学 | Lithium tungstate material, and preparation method and application thereof |
| CN106328918A (en) * | 2016-11-04 | 2017-01-11 | 中南大学 | NiTiO3/C compound material for sodium-ion battery, preparation method and application |
| CN107394128A (en) * | 2017-06-19 | 2017-11-24 | 厦门大学 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
| CN107845781A (en) * | 2016-09-19 | 2018-03-27 | 微宏动力***（湖州）有限公司 | Lithium ion secondary battery cathode active material, its preparation method and lithium rechargeable battery |
| CN108649196A (en) * | 2018-04-28 | 2018-10-12 | 河南工业大学 | Lithium vanadate combination electrode material and the preparation method and application thereof |
| CN108666541A (en) * | 2018-04-16 | 2018-10-16 | 华南理工大学 | A kind of sol-gel method preparation carbon coating VOMoO4The method of lithium ion battery negative material |
| RU2683094C1 (en) * | 2018-06-28 | 2019-03-26 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской акдемии наук | Method for obtaining composite of lithium orthovanadate / carbon |
| CN111834615A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-specific-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN112320845A (en) * | 2020-11-02 | 2021-02-05 | 四川大学 | Perovskite structure vanadate-based battery negative electrode active material |
| CN112374537A (en) * | 2020-11-02 | 2021-02-19 | 四川大学 | Preparation method of metal vanadate nano composite material |
| CN112960707A (en) * | 2021-03-31 | 2021-06-15 | 华南理工大学 | Nickel pyrovanadate as negative electrode material of lithium and sodium ion battery, and preparation method and application of nickel pyrovanadate in combination with sol-gel annealing |
| CN113603139A (en) * | 2021-08-24 | 2021-11-05 | 攀枝花学院 | LiVO3Electrode material and rapid preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154725A (en) * | 2006-09-19 | 2008-04-02 | 三星Sdi株式会社 | Negative active material for non-aqueous rechargeable battery, and non-aqueous rechargeable battery including same |
| CN101916852A (en) * | 2009-11-29 | 2010-12-15 | 宁波大学 | Preparation method of lithium ion battery anode material lithium vanadate with negative attenuation coefficient |
-
2013
- 2013-06-17 CN CN201310238638.4A patent/CN104241626B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154725A (en) * | 2006-09-19 | 2008-04-02 | 三星Sdi株式会社 | Negative active material for non-aqueous rechargeable battery, and non-aqueous rechargeable battery including same |
| CN101916852A (en) * | 2009-11-29 | 2010-12-15 | 宁波大学 | Preparation method of lithium ion battery anode material lithium vanadate with negative attenuation coefficient |
Non-Patent Citations (2)
| Title |
|---|
| HUIQIAO ET AL: ""Li3VO4：A promising Insertion Anode Material for Lithium-Ion Batteries"", 《ADV.ENERGY MATER》 * |
| 宋秀芹等: ""Li3VO4的非醇盐溶胶-凝胶法合成及其离子导电性"", 《材料导报》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681784B (en) * | 2015-02-10 | 2018-03-20 | 华中科技大学 | A kind of vanadic acid lithium titanate cathode material, negative pole, battery and cathode material preparation method |
| CN104681784A (en) * | 2015-02-10 | 2015-06-03 | 华中科技大学 | Lithium vanadate anode material, anode, battery and anode material preparation method |
| CN104934577B (en) * | 2015-05-15 | 2017-05-17 | 武汉理工大学 | Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material |
| CN104934577A (en) * | 2015-05-15 | 2015-09-23 | 武汉理工大学 | Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material |
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery |
| CN105529450A (en) * | 2016-03-02 | 2016-04-27 | 合肥国轩高科动力能源有限公司 | Preparation method for lithium ion battery cathode material fluorine-doped lithium vanadate with circulatory stability |
| CN106058217A (en) * | 2016-08-11 | 2016-10-26 | 复旦大学 | Lithium tungstate material, and preparation method and application thereof |
| CN106058217B (en) * | 2016-08-11 | 2019-08-09 | 复旦大学 | A kind of wolframic acid lithium material and its preparation and application |
| CN107845781A (en) * | 2016-09-19 | 2018-03-27 | 微宏动力***（湖州）有限公司 | Lithium ion secondary battery cathode active material, its preparation method and lithium rechargeable battery |
| CN107845781B (en) * | 2016-09-19 | 2022-01-18 | 微宏动力***（湖州）有限公司 | Negative electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| 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 |
| CN107394128A (en) * | 2017-06-19 | 2017-11-24 | 厦门大学 | A kind of novel cathode material for lithium ion battery and preparation method thereof |
| CN108666541A (en) * | 2018-04-16 | 2018-10-16 | 华南理工大学 | A kind of sol-gel method preparation carbon coating VOMoO4The method of lithium ion battery negative material |
| CN108666541B (en) * | 2018-04-16 | 2021-07-16 | 华南理工大学 | Sol-gel method for preparing carbon-coated VOMoO4Method for preparing lithium ion battery cathode material |
| CN108649196B (en) * | 2018-04-28 | 2021-03-16 | 河南工业大学 | Lithium vanadate composite electrode material and preparation method and application thereof |
| CN108649196A (en) * | 2018-04-28 | 2018-10-12 | 河南工业大学 | Lithium vanadate combination electrode material and the preparation method and application thereof |
| RU2683094C1 (en) * | 2018-06-28 | 2019-03-26 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской акдемии наук | Method for obtaining composite of lithium orthovanadate / carbon |
| CN111834615A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-specific-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN111834615B (en) * | 2019-04-23 | 2021-11-16 | 四川佰思格新能源有限公司 | Composite negative electrode material, preparation method and lithium ion battery |
| CN112320845A (en) * | 2020-11-02 | 2021-02-05 | 四川大学 | Perovskite structure vanadate-based battery negative electrode active material |
| CN112374537A (en) * | 2020-11-02 | 2021-02-19 | 四川大学 | Preparation method of metal vanadate nano composite material |
| CN113816422A (en) * | 2020-11-02 | 2021-12-21 | 四川大学 | Metal vanadate nanocomposite, preparation method thereof and lithium ion secondary battery |
| CN112320845B (en) * | 2020-11-02 | 2022-03-18 | 四川大学 | Perovskite structure vanadate-based battery negative electrode active material |
| CN112960707A (en) * | 2021-03-31 | 2021-06-15 | 华南理工大学 | Nickel pyrovanadate as negative electrode material of lithium and sodium ion battery, and preparation method and application of nickel pyrovanadate in combination with sol-gel annealing |
| CN113603139A (en) * | 2021-08-24 | 2021-11-05 | 攀枝花学院 | LiVO3Electrode material and rapid preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104241626B (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104241626B (en) | The process for preparing sol-gel of lithium ion battery lithium vanadate negative material | |
| US11855285B2 (en) | Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof | |
| Tang et al. | Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2 | |
| CA2623636C (en) | Method of producing positive electrode active material and nonaqueous electrolyte battery using same | |
| Zhao et al. | Synthesis and electrochemical characterization of Zn-doped Li-rich layered Li [Li0. 2Mn0. 54Ni0. 13Co0. 13] O2 cathode material | |
| CN109546123B (en) | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof | |
| CN109119624B (en) | Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material | |
| CN103943827A (en) | High-temperature solid-phase preparation method of negative electrode material lithium orthosilicate of lithium ion battery | |
| Yi et al. | High-performance xLi2MnO3·(1-x) LiMn1/3Co1/3Ni1/3O2 (0.1 x 0.5) as Cathode Material for Lithium-ion Battery | |
| CN103441263B (en) | The method of a kind of collosol and gel-solid sintering technology synthesis nickle cobalt lithium manganate | |
| CN104241625A (en) | Lithium ion battery cathode material lithium vanadate and preparation method thereof | |
| CN113479944A (en) | Preparation method of modified high-nickel ternary cathode material | |
| CN111115713A (en) | LaMnO3Coated lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN104022282A (en) | High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate | |
| WO2024055516A1 (en) | Method for preparing lithium manganese iron phosphate positive electrode material by means of spray combustion and use thereof | |
| WO2024055519A1 (en) | Preparation method and use of lithium manganese iron phosphate | |
| CN106025182A (en) | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof | |
| CN112186166B (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| TWI550938B (en) | Cathode material of lithium ion battery and method for making the same | |
| CN114864894B (en) | High-pressure-resistant coating modified lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| GB2621290A (en) | Template growth method for preparing lithium cobaltate precursor and use thereof | |
| CN114203993B (en) | Li (lithium ion battery) 2 SeO 4 Fast ion conductor modified lithium ion battery anode material | |
| CN102983333A (en) | Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |