CN107742700A - A kind of preparation method of carbon coating titanium lithium composite negative pole material - Google Patents
A kind of preparation method of carbon coating titanium lithium composite negative pole material Download PDFInfo
- Publication number
- CN107742700A CN107742700A CN201710850031.XA CN201710850031A CN107742700A CN 107742700 A CN107742700 A CN 107742700A CN 201710850031 A CN201710850031 A CN 201710850031A CN 107742700 A CN107742700 A CN 107742700A
- Authority
- CN
- China
- Prior art keywords
- lithium
- composite
- solution
- titanium
- negative pole
- 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.)
- Pending
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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 discloses a kind of preparation method of carbon coating titanium lithium composite negative pole material, methods described is by hydro-thermal method, by Al3+And Cr3+In lattice structure according to certain ratio incorporation lithium titanate, the novel anode material synthesized with such a method is still spinel structure, has widened the diffusion admittance of lithium ion, reduces the diffusional resistance of lithium ion so as to improve the ionic conductivity of material；The present invention improves the electric conductivity of active material by the compound of carbon, in addition, the expansion of volume provides the useful space when carbon-coating cavity is active material Li insertion extraction, it is therefore prevented that the efflorescence reunion of negative material.
Description
Technical field
The present invention relates to battery material field, and in particular to a kind of preparation method of carbon coating titanium lithium composite negative pole material.
Background technology
In recent years, domestic new-energy automobile industry development is rapid, and battery variety is rich and varied, market to the demand of battery and
It is required that gradually increase.Its most concerned key index is concentrated mainly on five broad aspects：Safety and stability performance, cycle life, resistance to width
Warm nature, charging rate and energy density.
In recent years, graphite is widely used in a variety of applications as lithium ion battery negative material, is current commercial Li-ion
The main flow negative material of battery, with the continuous modification of researcher, performance than having a larger improvement during initially application, but its
It is relatively low there are still theoretical capacity（372 mAh g-1）The defects of, limit the further application of lithium ion battery.Transition gold
Category oxide due to its higher reversible capacity obtained it is widely studied.
It is extensive that the plurality of advantages of lithium titanate makes it have in fields such as electric automobile, hybrid vehicle and energy-storage batteries
Application prospect.But Li4Ti5O12The electronic conductivity of material is low to cause its chemical property under high magnification poor, and
Flatulence problem can be produced in battery charge and discharge process, these have all severely impacted the cycle life of battery, and limit titanium
The practical application of sour lithium.
The content of the invention
The present invention provides a kind of preparation method of carbon coating titanium lithium composite negative pole material, and methods described, will by hydro-thermal method
Al3+And Cr3+In lattice structure according to certain ratio incorporation lithium titanate, the novel anode material synthesized with such a method is still
Be spinel structure, widened the diffusion admittance of lithium ion, reduce the diffusional resistance of lithium ion so as to improve material from
Electron conductivity；The present invention improves the electric conductivity of active material by the compound of carbon, in addition, carbon-coating cavity be active material it is embedding/
The expansion of volume provides the useful space during de- lithium, it is therefore prevented that the efflorescence of negative material is reunited.
To achieve these goals, the present invention provides a kind of preparation method of carbon coating titanium lithium composite negative pole material, the party
Method comprises the following steps：
（1）Prepare composite titanic acid lithium material
The molecular formula of the composite lithium titanate is Li4-xTi4AlxCrO12, wherein 0.95≤x≤1.05；
Butyl titanate is dissolved in ethylene glycol solution and forms titanium solution；
Lithium citrate, aluminium chloride, chromic nitrate are added in deionized water, are configured to mixed solution；
Under stirring, mixed solution is added in titanium solution, is sufficiently mixed uniform composite solution；
Composite solution is transferred in reactor, 25-30h is heated under the conditions of 180-195 DEG C, before being obtained after filtering and drying
Drive body；
By presoma in air atmosphere, temperature be 600-800 DEG C under conditions of calcine 8-10h, obtain composite lithium titanate；
（2）Composite titanic acid lithium material after washing is scattered in 80 parts by weight of deionized water, then adds 0.3-0.35 parts by weight
Pyrrole monomer, ultrasonic 45-50min, then the initiator that 50 parts by weight concentration are 20-25mmol/L is added dropwise under agitation
Solution, last polymerisation 4-12h, centrifugation, washing, dry；
（3）The dried product is placed in atmosphere of inert gases, 570 are warming up to 5 DEG C -8 DEG C/min heating rate
DEG C -630 DEG C, anneal 1-3h, polypyrrole is carbonized；Obtain carbon coating titanium lithium composite negative pole material.
Preferably, the titanium, lithium, aluminium, the element molal weight ratio of chromium are 4：(2.95-3.05)：(0.95-1.05)：1.
The invention has the advantages that and remarkable result：
（1）Methods described is by hydro-thermal method, by Al3+And Cr3+In lattice structure according to certain ratio incorporation lithium titanate, use
The novel anode material of such a method synthesis is still spinel structure, has widened the diffusion admittance of lithium ion, has reduced lithium ion
Diffusional resistance so as to improving the ionic conductivity of material；
（2）The present invention improves the electric conductivity of active material by the compound of carbon, in addition, carbon-coating cavity is that active material is embedding/de-
The expansion of volume provides the useful space during lithium, it is therefore prevented that the efflorescence of negative material is reunited.
Embodiment
Embodiment one
The molecular formula of the composite lithium titanate is Li3.05Ti4Al0.95CrO12。
Butyl titanate is dissolved in ethylene glycol solution and forms titanium solution；Lithium citrate, aluminium chloride, chromic nitrate are added and gone
In ionized water, mixed solution is configured to；Under stirring, mixed solution is added in titanium solution, is sufficiently mixed uniform obtain
Composite solution；The titanium, lithium, aluminium, the element molal weight ratio of chromium are 4：3.05：0.95：1.
Composite solution is transferred in reactor, 25h is heated under the conditions of 180 DEG C, forerunner is obtained after filtering and drying
Body；By presoma in air atmosphere, temperature be 600 DEG C under conditions of calcine 8h, obtain composite lithium titanate.
Composite titanic acid lithium material after washing is scattered in 80 parts by weight of deionized water, then adds 0.3 parts by weight pyrroles
Monomer, ultrasonic 45min, then the initiator solution that 50 parts by weight concentration are 20mmol/L is added dropwise under agitation, finally
Polymerisation 4h, centrifugation, washing, dry.
The dried product is placed in atmosphere of inert gases, 570 DEG C are warming up to 5 DEG C/min heating rate,
Anneal 1h, polypyrrole is carbonized；Obtain carbon coating titanium lithium composite negative pole material.
Embodiment two
The molecular formula of the composite lithium titanate is Li2.95Ti4Al1.05CrO12。
Butyl titanate is dissolved in ethylene glycol solution and forms titanium solution；Lithium citrate, aluminium chloride, chromic nitrate are added and gone
In ionized water, mixed solution is configured to；Under stirring, mixed solution is added in titanium solution, is sufficiently mixed uniform obtain
Composite solution；The titanium, lithium, aluminium, the element molal weight ratio of chromium are 4：2.95：1.05：1.
Composite solution is transferred in reactor, 30h is heated under the conditions of 195 DEG C, forerunner is obtained after filtering and drying
Body；By presoma in air atmosphere, temperature be 800 DEG C under conditions of calcine 10h, obtain composite lithium titanate.
Composite titanic acid lithium material after washing is scattered in 80 parts by weight of deionized water, then adds 0.35 parts by weight pyrroles
Monomer, ultrasonic 50min, then the initiator solution that 50 parts by weight concentration are 25mmol/L is added dropwise under agitation, finally
Polymerisation 12h, centrifugation, washing, dry.
The dried product is placed in atmosphere of inert gases, 630 DEG C are warming up to 8 DEG C/min heating rate,
Anneal 3h, polypyrrole is carbonized；Obtain carbon coating titanium lithium composite negative pole material.
Using above-described embodiment one, two products therefrom materials as being used for cathode of lithium battery, with just extremely LiFePO 4 material
The test battery pack of composition carries out cyclical stability test, and discharge capacity is respectively 535.2mAh/g and 526.2mAh/g first,
Capacity is 437.1mAh/g and 424.5mAh/g after circulating 200 times, has good cyclical stability.
Claims (2)
1. a kind of preparation method of carbon coating titanium lithium composite negative pole material, this method comprise the following steps：
（1）Prepare composite titanic acid lithium material
The molecular formula of the composite lithium titanate is Li4-xTi4AlxCrO12, wherein 0.95≤x≤1.05；
Butyl titanate is dissolved in ethylene glycol solution and forms titanium solution；
Lithium citrate, aluminium chloride, chromic nitrate are added in deionized water, are configured to mixed solution；
Under stirring, mixed solution is added in titanium solution, is sufficiently mixed uniform composite solution；
Composite solution is transferred in reactor, 25-30h is heated under the conditions of 180-195 DEG C, before being obtained after filtering and drying
Drive body；
By presoma in air atmosphere, temperature be 600-800 DEG C under conditions of calcine 8-10h, obtain composite lithium titanate；
（2）Composite titanic acid lithium material after washing is scattered in 80 parts by weight of deionized water, then adds 0.3-0.35 parts by weight
Pyrrole monomer, ultrasonic 45-50min, then the initiator that 50 parts by weight concentration are 20-25mmol/L is added dropwise under agitation
Solution, last polymerisation 4-12h, centrifugation, washing, dry；
（3）The dried product is placed in atmosphere of inert gases, 570 are warming up to 5 DEG C -8 DEG C/min heating rate
DEG C -630 DEG C, anneal 1-3h, polypyrrole is carbonized；Obtain carbon coating titanium lithium composite negative pole material.
2. the method as described in claim 1, it is characterised in that the titanium, lithium, aluminium, the element molal weight ratio of chromium are 4：
(2.95-3.05)：(0.95-1.05)：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710850031.XA CN107742700A (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710850031.XA CN107742700A (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107742700A true CN107742700A (en) | 2018-02-27 |
Family
ID=61235995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710850031.XA Pending CN107742700A (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107742700A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816595A (en) * | 2017-03-09 | 2017-06-09 | 合肥工业大学 | A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon |
| CN106992289A (en) * | 2017-04-16 | 2017-07-28 | 合肥国轩高科动力能源有限公司 | A kind of synthetic method of titanium magnesium lithium chromate and its application as lithium ion battery negative material |
-
2017
- 2017-09-15 CN CN201710850031.XA patent/CN107742700A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816595A (en) * | 2017-03-09 | 2017-06-09 | 合肥工业大学 | A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon |
| CN106992289A (en) * | 2017-04-16 | 2017-07-28 | 合肥国轩高科动力能源有限公司 | A kind of synthetic method of titanium magnesium lithium chromate and its application as lithium ion battery negative material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104577119B (en) | Preparation method of cathode material LiMn1-xFexPO4 for lithium ion cell | |
| CN103413924B (en) | A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof | |
| CN107437617B (en) | A kind of surface modification method, gained richness lithium material and application improving rich lithium material chemical property | |
| CN109599593B (en) | Method for preparing solid-state battery with multilayer composite electrolyte | |
| CN109768279A (en) | A kind of combined conductive agent and preparation method thereof, lithium ion cell positive | |
| CN106876686A (en) | A kind of method for carrying out surface modification with positive electrode active materials to lithium ion battery | |
| CN105789606A (en) | Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material | |
| CN114229816B (en) | Method for recycling and preparing anode material from waste lithium iron phosphate battery | |
| CN101339992A (en) | Preparation of lithium ionic cell positive electrode material vanadium lithium silicate | |
| CN103000874A (en) | Preparation method of carbon-coated ternary positive electrode material | |
| CN105428628A (en) | Preparation method of porous spherical high-voltage lithium ion battery positive electrode material | |
| CN108054350A (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN111056544B (en) | Sodium iron phosphate composite material and preparation method and application thereof | |
| JP2002151083A (en) | Manufacturing method of positive pole active material for lithium secondary battery | |
| CN104485443B (en) | A kind of graphene polymer coats the preparation method of niobium cation doping lithium aluminate composite positive pole | |
| CN109301223A (en) | Anode composite material of lithium sulfur battery and preparation method thereof | |
| CN110350173B (en) | Lithium-sulfur soft package battery and preparation method thereof | |
| CN107742710A (en) | A kind of preparation method of chromium base lithium ion battery composite cathode material | |
| CN106684347A (en) | Polypyrrole-coated cobalt manganese oxide coaxial nanowire, and preparation method and application thereof | |
| CN107742708B (en) | Preparation method of polymer-coated composite positive electrode material | |
| CN107799734A (en) | A kind of preparation method of ferro-aluminum doped titanic acid lithium titanate cathode material | |
| CN113178614B (en) | Composite solid electrolyte, solid lithium battery and preparation method | |
| CN107742700A (en) | A kind of preparation method of carbon coating titanium lithium composite negative pole material | |
| CN112490440B (en) | Liquid phase reaction prepared oxyselenide/sulfoselenide, method and application thereof | |
| CN104600261B (en) | Graphite/Mn3O4 composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180227 |