CN104319396A - Preparation method of surface cladding material of lithium ion battery cathode material - Google Patents

Preparation method of surface cladding material of lithium ion battery cathode material Download PDF

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Publication number
CN104319396A
CN104319396A CN201410483294.8A CN201410483294A CN104319396A CN 104319396 A CN104319396 A CN 104319396A CN 201410483294 A CN201410483294 A CN 201410483294A CN 104319396 A CN104319396 A CN 104319396A
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China
Prior art keywords
metal ion
preparation
lithium
manganese
mol ratio
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CN201410483294.8A
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Chinese (zh)
Inventor
孙琦
李岩
孙慧英
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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Priority to CN201410483294.8A priority Critical patent/CN104319396A/en
Publication of CN104319396A publication Critical patent/CN104319396A/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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 surface cladding material of a lithium ion battery cathode material and a preparation method thereof. Through a mixed sol preparation mode, the surface of the lithium ion battery anode material (such as LiCoO2) is uniformly coated with a layer of metal ion doped TiO2 thin film. The metal ion doped TiO2 thin film improves the discharge platform, for the first time efficiency and discharge capacity of the anode material, while improving cycle performance and rate performance of anode material under high voltage, also has the advantages of simple preparation process and low cost, and is suitable for industrialized mass production.

Description

A kind of Surface coating material of anode material for lithium-ion batteries and preparation method
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, be specifically related to the Surface coating material of anode material for lithium-ion batteries, and be coated with the preparation method of anode material for lithium-ion batteries of this material.
Background technology
Anode material for lithium-ion batteries is widely used in the electronic equipments such as notebook, mobile phone, digital camera and electric motor car.Along with the demand of market to anode material for lithium-ion batteries increases day by day, the requirement in material capacity, security performance and cycle performance is also more and more higher.
With cobalt acid lithium (LiCoO 2) be example, cobalt acid lithium is commercial li-ion cell positive material the most conventional at present, and its theoretical capacity is 274mAhg -1, but actual capacity does not but reach so high far away.LiCoO 2time between 3 ~ 4.2V with 0.1C discharge and recharge, actual capacity is 140mAhg -1left and right.This is due to when being charged to 4.2V, and deviating from of corresponding lithium ion, material structure is changed to Li 1-xcoO 2(0≤x≤0.5), only has the lithium ion of nearly half to deviate from.In order to improve LiCoO 2the capacity of battery, charging voltage needs more than 4.2V, makes to deviate from more lithium ion in structure.But, when improving end of charge voltage, LiCoO 2α-NaFeO 2in lattice, c-axis direction can be expanded, thus destroys the structure of its script, causes capacity to decline, and is attended by cobalt dissolving in the electrolytic solution.There are some researches show, battery end of charge voltage is higher, and electricity conversion efficiency is lower, and electrode activity decay is also more serious.In order to improve LiCoO 2electrical property under high voltages, can under its Surface coating layer of material stops high voltage LiCoO 2the expansion of structure and the dissolving of cobalt.
Current anode material for lithium-ion batteries is coated is generally adopt single a kind of material to carry out coated, such as application number is the Chinese invention patent application " the Surface coating material and progress of lithium ion cell positive " of 200310122880.1, its coated method mainly makes metallic salt as hydrolysis such as aluminium salt, zinc salts, then heat-treats with positive electrode mixing again.Aluminium salt etc. can improve the cycle performance of material effectively, but can not improve platform and the efficiency first of material, and does not have the speed of effective measures controlled hydrolysis, easily generates precipitation and makes coated uneven.
Summary of the invention
First object of the present invention is the deficiency of the clad material overcoming anode material for lithium-ion batteries in prior art, a kind of clad material for anode material for lithium-ion batteries is provided, under improvement is compared with high charge-discharge voltage while anode material for lithium-ion batteries cycle performance, improve discharge platform and the efficiency first of material.
Technical scheme of the present invention is as follows:
For a Surface coating material for anode material for lithium-ion batteries, it is the titanium deoxid film doped with metal ion manganese; The mol ratio of described metal ion manganese and Ti is 6: 1 ~ 7: 1; Described anode material for lithium-ion batteries is nickle cobalt lithium manganate.
A preparation method for metal ion doped titanium dioxide coated lithium ion battery positive electrode, comprises the following steps:
1) titanium source compound and beta-diketon class stabilizer are mixed to form solution, or their dissolvings are formed solution in a solvent;
2) compound containing metal ion manganese or its solution are added step 1) in gained solution, the fully obtained colloidal sol of mixing;
3) being that the mol ratio of 0.06: 1 ~ 0.1: 1 is by step 2 according to Ti with nickle cobalt lithium manganate) gained colloidal sol fully mixes with nickle cobalt lithium manganate, then removes solvent, drying, obtain mixed material;
4) by step 3) heat treatment 1 ~ 2 hour at 1250 ~ 1300 DEG C of gained mixed material, with stove cooling, namely obtain the coated nickel-cobalt lithium manganate material of metal ion doped titanium dioxide.
Further, step 1) described in titanium source compound be tetrabutyl titanate and/or tetraethyl titanate; Described beta-diketon class stabilizer be selected from ethyl acetoacetate, acetylacetone,2,4-pentanedione and benzoyl acetone one or more.
Further, step 1) described in the mol ratio of Ti in titanium source compound and beta-diketon class stabilizer be 2.5: 1 ~ 3: 1.
Further, step 2) the described compound containing metal ion manganese is metallic salt or its oxide, metallorganic.
Further, the mol ratio of described metal ion manganese and Ti is 6: 1 ~ 7: 1.
Technical conceive of the present invention is the mode by preparing mixed sols, at nickel-cobalt lithium manganate material coated with uniform last layer metal ion doped titanium dioxide film.Metal ion doped titanium dioxide film on the one hand prevents electrolyte to the dissolved corrosion of inner active substances in cathode materials, thus improves the fail safe of positive electrode, cycle performance and high rate performance; On the other hand, the introducing of Titanium can improve discharge platform, first efficiency and the discharge capacity of anode material for lithium-ion batteries.
In addition, the present invention is uniform and stable by the grain diameter little (< 10nm) of mixed sols that adopts the method for adding beta-diketon class stabilizer and prepare, is conducive to forming coating layer in anode material for lithium-ion batteries surface uniform precipitation.
The coated anode material for lithium-ion batteries of metal ion doped titanium dioxide prepared by the present invention has higher discharge platform, first efficiency and compacted density, greatly improves cycle performance and the high rate performance of material under high voltage simultaneously.The coated LiCoO of metal ion doped titanium dioxide of the present invention 2material electrochemical test is at 3 ~ 4.5V, and carry out reversible capability of charging and discharging for 188.6mAh/g with 35mA/g (0.2C), efficiency is 94.3% first, carries out the initial reversible capacity of discharge and recharge for 169.2mAh/g with 175mA/g (1C).Preparation method's technique of the anode material for lithium-ion batteries that this metal ion doped titanium dioxide is coated is simple, with low cost, is applicable to industrialization large-scale production.
Embodiment
Embodiment 1:
For a Surface coating material for anode material for lithium-ion batteries, it is the titanium deoxid film doped with metal ion manganese; The mol ratio of described metal ion manganese and Ti is 6: 1; Described anode material for lithium-ion batteries is nickle cobalt lithium manganate.
A preparation method for metal ion doped titanium dioxide coated lithium ion battery positive electrode, comprises the following steps:
1) titanium source compound and beta-diketon class stabilizer are mixed to form solution, or their dissolvings are formed solution in a solvent;
2) compound containing metal ion manganese or its solution are added step 1) in gained solution, the fully obtained colloidal sol of mixing;
3) being that the mol ratio of 0.1: 1 is by step 2 according to Ti with nickle cobalt lithium manganate) gained colloidal sol fully mixes with nickle cobalt lithium manganate, then removes solvent, drying, obtain mixed material;
4) by step 3) heat treatment 2 hours at 1250 DEG C of gained mixed material, with stove cooling, namely obtain the coated nickel-cobalt lithium manganate material of metal ion doped titanium dioxide.
Further, step 1) described in titanium source compound be tetrabutyl titanate and/or tetraethyl titanate; Described beta-diketon class stabilizer be selected from ethyl acetoacetate, acetylacetone,2,4-pentanedione and benzoyl acetone one or more.
Step 1) described in the mol ratio of Ti in titanium source compound and beta-diketon class stabilizer be 2.5: 1.
Step 2) the described compound containing metal ion manganese is metallic salt.
The mol ratio of described metal ion manganese and Ti is 7: 1.
Embodiment 2:
For a Surface coating material for anode material for lithium-ion batteries, it is the titanium deoxid film doped with metal ion manganese; The mol ratio of described metal ion manganese and Ti is 7: 1; Described anode material for lithium-ion batteries is nickle cobalt lithium manganate.
A preparation method for metal ion doped titanium dioxide coated lithium ion battery positive electrode, comprises the following steps:
1) titanium source compound and beta-diketon class stabilizer are mixed to form solution, or their dissolvings are formed solution in a solvent;
2) compound containing metal ion manganese or its solution are added step 1) in gained solution, the fully obtained colloidal sol of mixing;
3) being that the mol ratio of 0.06: 1 is by step 2 according to Ti with nickle cobalt lithium manganate) gained colloidal sol fully mixes with nickle cobalt lithium manganate, then removes solvent, drying, obtain mixed material;
4) by step 3) heat treatment 1 hour at 1300 DEG C of gained mixed material, with stove cooling, namely obtain the coated nickel-cobalt lithium manganate material of metal ion doped titanium dioxide.
Further, step 1) described in titanium source compound be tetrabutyl titanate and/or tetraethyl titanate; Described beta-diketon class stabilizer be selected from ethyl acetoacetate, acetylacetone,2,4-pentanedione and benzoyl acetone one or more.
Step 1) described in the mol ratio of Ti in titanium source compound and beta-diketon class stabilizer be 3: 1.
Step 2) the described compound containing metal ion manganese is metallorganic.
The mol ratio of described metal ion manganese and Ti is 6: 1.

Claims (6)

1., for a Surface coating material for anode material for lithium-ion batteries, be the titanium deoxid film doped with metal ion manganese; The mol ratio of described metal ion manganese and Ti is 6: 1 ~ 7: 1; Described anode material for lithium-ion batteries is nickle cobalt lithium manganate.
2. a preparation method for metal ion doped titanium dioxide coated lithium ion battery positive electrode, comprises the following steps:
1) titanium source compound and beta-diketon class stabilizer are mixed to form solution, or their dissolvings are formed solution in a solvent;
2) compound containing metal ion manganese or its solution are added step 1) in gained solution, the fully obtained colloidal sol of mixing;
3) being that the mol ratio of 0.06: 1 ~ 0.1: 1 is by step 2 according to Ti with nickle cobalt lithium manganate) gained colloidal sol fully mixes with nickle cobalt lithium manganate, then removes solvent, drying, obtain mixed material;
4) by step 3) heat treatment 1 ~ 2 hour at 1250 ~ 1300 DEG C of gained mixed material, with stove cooling, namely obtain the coated nickel-cobalt lithium manganate material of metal ion doped titanium dioxide.
3. preparation method as claimed in claim 2, is characterized in that: step 1) described in titanium source compound be tetrabutyl titanate and/or tetraethyl titanate; Described beta-diketon class stabilizer be selected from ethyl acetoacetate, acetylacetone,2,4-pentanedione and benzoyl acetone one or more.
4. preparation method as claimed in claim 2, is characterized in that, step 1) described in the mol ratio of Ti in titanium source compound and beta-diketon class stabilizer be 2.5: 1 ~ 3: 1.
5. preparation method as claimed in claim 2, is characterized in that, step 2) the described compound containing metal ion manganese is metallic salt or its oxide, metallorganic.
6. preparation method as claimed in claim 5, it is characterized in that, the mol ratio of described metal ion manganese and Ti is 6: 1 ~ 7: 1.
CN201410483294.8A 2014-09-19 2014-09-19 Preparation method of surface cladding material of lithium ion battery cathode material Pending CN104319396A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107473265A (en) * 2017-08-25 2017-12-15 金川集团股份有限公司 A kind of method of powder body material cladding titanium dioxide
CN107658439A (en) * 2017-08-30 2018-02-02 格林美（无锡）能源材料有限公司 Lithium ion tertiary cathode material that a kind of tungsten titanium coats altogether and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107473265A (en) * 2017-08-25 2017-12-15 金川集团股份有限公司 A kind of method of powder body material cladding titanium dioxide
CN107473265B (en) * 2017-08-25 2019-04-26 金川集团股份有限公司 A kind of method of powder body material cladding titanium dioxide
CN107658439A (en) * 2017-08-30 2018-02-02 格林美（无锡）能源材料有限公司 Lithium ion tertiary cathode material that a kind of tungsten titanium coats altogether and preparation method thereof

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