CN104617262A - Multivariate material composite positive electrode and lithium ion battery - Google Patents

Multivariate material composite positive electrode and lithium ion battery Download PDF

Info

Publication number
CN104617262A
CN104617262A CN201410779893.4A CN201410779893A CN104617262A CN 104617262 A CN104617262 A CN 104617262A CN 201410779893 A CN201410779893 A CN 201410779893A CN 104617262 A CN104617262 A CN 104617262A
Authority
CN
China
Prior art keywords
positive electrode
lithium ion
material compound
ion battery
multicomponent material
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
Application number
CN201410779893.4A
Other languages
Chinese (zh)
Other versions
CN104617262B (en
Inventor
马伟华
颜雪冬
毛德来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Veken Battery Co., Ltd.
Original Assignee
NINGBO VEKEN BATTERY CO Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NINGBO VEKEN BATTERY CO Ltd filed Critical NINGBO VEKEN BATTERY CO Ltd
Priority to CN201410779893.4A priority Critical patent/CN104617262B/en
Publication of CN104617262A publication Critical patent/CN104617262A/en
Application granted granted Critical
Publication of CN104617262B publication Critical patent/CN104617262B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • H01M4/48—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
    • H01M4/36—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
    • 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 the technical field of lithium ion batteries, and specifically relates a multivariate material composite positive electrode and a lithium ion battery. The multivariate material composite positive electrode material chemical combination formula is as follows: LixNaaTibCocMndAleNyO4, 0.20 <= x <= 0.25, 0.05 <= a<= 0.1, 0.15<= b <= 0.35, 0.54 <=c<= 68, 0.48 <= d <= 0.69, 0.40 <=e <=0.55 and 0.01<= y<= 0.13. The positive electrode material has high energy density, good cycling performance, high ratio and long cycle life.

Description

A kind of positive pole of multicomponent material compound and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of positive pole and lithium ion battery of multicomponent material compound.
Background technology
Along with developing rapidly of battery industry, in order to solve useful life of battery, energy density, the problems such as self discharge or quality, there is various types of battery.At present, because lithium battery has the advantages such as energy density is high, long service life, quality are light, self discharge is little, now become the first-selected power supply of the portable set such as communication apparatus, notebook computer, and also started to be applied in the medium-and-large-sized equipment such as electric motor car, national defence.Light-duty and compact electronic device can have been made extensively to distribute based on the high-energy-density of reversible some material of embedding of lithium and long-life rechargeable battery, described electronic installation is as mobile phone and portable computer.But some anode material, as LiCoO 2application cause worry, reason is the toxicity of cobalt, due to oxygen discharge fire and the blast caused danger and in overcharge or in the temperature raised time and the vigorous reaction (thermal runaway) of organic bath.And cobalt is quite rare and be therefore expensive element.Other material, as LiMn 2o 4there are poor long-time stability.
Since first lithium ion battery being positive electrode with cobalt acid lithium (LiCoO2) successfully comes out, the research of various countries experts and scholars to anode material for lithium-ion batteries deepens continuously, success is studied and has prepared other transiting metal oxidation positive electrodes, as lithium nickelate (LiNiO2), LiMn2O4 (LiMnO2), LiFePO4 (LiFePO4) etc.Subsequently, the multi-element composite positive pole material of multiple elements design solid solution and rich lithium is proposed, as LiNi0.33Co0.33Mn0.33O2, Li1.2Ni0.13Co0.13Mn0.54O2 etc.In recent years, it is found that other positive electrodes of capacity relative of the multi-element composite positive pole material of rich lithium, there is obvious advantage, certain achievement is obtained to its research.
Since tertiary cathode material LixNiaCobMncO2 self-discovery, (can up to 250mAh/g because it has that capacity is high, for 91% of theoretical capacity), the advantage such as security performance is excellent and cheap, receive extensive concern and the research of people, and be widely used.
Along with the development of current new-energy automobile industry and the requirement both at home and abroad to vehicle environmental protection, low emission, progressively become the main flow of new-energy automobile as the pure electric automobile of energy supply main body, hybrid vehicle using lithium ion battery.LiFePO4, due to advantages such as its cost of material are low, fail safe is good and the life-span is long, first enters the sight line of researcher.But along with the requirement of car load field to electric automobile course continuation mileage, high/low temperature power-performance, homogeneity of product improves constantly, stratiform multi-element composite material progressively becomes the main flow positive electrode of car load field electrokinetic cell.For power-type lithium ion battery field, positive electrode, while ensureing enough energy densities, also needs to pay close attention to high rate performance to guarantee the high-power output of battery, pays close attention to the cycle life of material to guarantee the long-time Reusability of battery.Thus developing the positive electrode of high magnification long circulation life, especially multicomponent composite oxide material, is exactly a very important problem.
CN 101630736A discloses and a kind ofly improves improving one's methods of nickel-cobalt-manganternary ternary anode material cycle performance, carry out detection to tertiary cathode material first to analyze, obtain lithium carbonate residual volume, add TiO2 according to lithium carbonate residual volume proportioning, be less than the tertiary cathode material be obtained by reacting at 900 DEG C containing Li2TiO3 at high temperature.But owing to there being the introducing of TiO2 in the reaction, TiO2 is a kind of more active material, the decomposition of electrolyte will be caused, if the lithium carbonate of TiO2 and remaining 1000ppm level reacts not thorough, will the problem that there is high temperature inflatable containing the tertiary cathode material of Li2TiO3 be caused.
Summary of the invention
The object of the invention is to solve the problem, a kind of positive pole and lithium ion battery of multicomponent material compound are provided.Lithium ion battery prepared by the present invention is while maintaining high-energy-density, and its cycle life is longer.
In order to reach foregoing invention object, the present invention by the following technical solutions:
A positive electrode for multicomponent material compound, the chemical combination formula of described positive electrode is:
Li xna ati bco cmn dal en yo 4wherein 0.20≤x≤0.25,0.05 < a < 0.1,0.15 < b < 0.35,0.54 < c < 68,0.48 < d < 0.69,0.40 < e < 0.55,0.01≤y≤0.13.
As preferably, the preparation method of described positive electrode is, according to Li, Na, Ti, Co, Mn, Al, the mole of N and O takes lithia, sodium carbonate, titanium trichloride, nickel cobalt manganese, the sub-manganese of acetic acid and aluminium hydroxide, and add the lanthana of 2% of each component gross mass, enter to grind 10-15h in ball mill, then in the mixture obtained, add the sucrose accounting for its quality 10%, the carbon black of 5% and the acetone of 300%, form mixed liquor, then mixture is adopted ball mill grinding 3-5h, by the mixture centrifugation obtained, and at 500 DEG C, process 10-30min by being separated the solids obtained, then at 800-850 DEG C, 1-2h is processed, then 900-950 DEG C of sintering 3-5h is heated to, naturally cooling obtains product.
As preferably, in mixed liquor, add NaOH regulate pH to be 8-9.
As preferably, separation is obtained solids and process 10min at 500 DEG C, then at 800 DEG C, process 1h, be then heated to 950 DEG C of sintering 4h, cooling obtains product naturally.
A kind of lithium ion battery, lithium ion battery adopts the positive electrode of above-mentioned a kind of multicomponent material compound to be prepared from.
Compared with prior art, beneficial effect is in the present invention:
1 energy density is higher and cycle performance excellent;
2 these positive electrodes have high magnification and long circulation life.
Embodiment
Below by specific embodiment, explanation is further described to technical scheme of the present invention.
If without specified otherwise, the raw material adopted in embodiments of the invention is the conventional raw material in this area, and the method adopted in embodiment, is the conventional method of this area.
Embodiment 1:
A kind of preparation of positive electrode of multicomponent material compound:
The chemical combination formula of positive electrode to be prepared is Li xna ati bco cmn dal en yo 4wherein 0.20≤x≤0.25,0.05 < a < 0.1,0.15 < b < 0.35,0.54 < c < 0.68,0.48 < d < 0.69,0.40 < e < 0.55,0.01≤y≤0.13.
According to Li, Na, Ti, Co, Mn, Al, the mole of N and O takes lithia, sodium carbonate, titanium trichloride, nickel cobalt manganese, the sub-manganese of acetic acid and aluminium hydroxide, mole is respectively: 2.3, 0.6, 2, 6, 5, 4.5 and 0.8, and add the lanthana of 2% of each component gross mass, enter to grind 10-15h in ball mill, then in the mixture obtained, add the sucrose accounting for its quality 10%, the carbon black of 5% and the acetone of 300%, form mixed liquor, then mixture is adopted ball mill grinding 3-5h, by the mixture centrifugation obtained, and at 500 DEG C, process 10-30min by being separated the solids obtained, then at 800-850 DEG C, 1-2h is processed, then 900-950 DEG C of sintering 3-5h is heated to, naturally cooling obtains product.
Embodiment 2:
A kind of preparation of positive electrode of multicomponent material compound:
The chemical combination formula of positive electrode to be prepared is Li xna ati bco cmn dal en yo 4wherein 0.20≤x≤0.25,0.05 < a < 0.1,0.15 < b < 0.35,0.54 < c < 68,0.48 < d < 0.69,0.40 < e < 0.55,0.01≤y≤0.13.
According to Li, Na, Ti, Co, Mn, Al, the mole of N and O takes lithia, sodium carbonate, titanium trichloride, nickel cobalt manganese, the sub-manganese of acetic acid and aluminium hydroxide, , mole is respectively: 2.2, 0.65, 2.2, 6.5, 5.4, 4.3 and 0.9, and add the lanthana of 2% of each component gross mass, enter to grind 10-15h in ball mill, then in the mixture obtained, add the sucrose accounting for its quality 10%, the carbon black of 5% and the acetone of 300%, form mixed liquor, and add NaOH regulate pH be 8-9, then mixture is adopted ball mill grinding 3-5h, by the mixture centrifugation obtained, and at 500 DEG C, process 30min by being separated the solids obtained, then at 800 DEG C, 2h is processed, then 950 DEG C of sintering 5h are heated to, naturally cooling obtains product.
This product is adopted to prepare lithium ion battery.
Embodiment 3:
A kind of preparation of positive electrode of multicomponent material compound:
The chemical combination formula of positive electrode to be prepared is Li xna ati bco cmn dal en yo 4wherein 0.20≤x≤0.25,0.05 < a < 0.1,0.15 < b < 0.35,0.54 < c < 68,0.48 < d < 0.69,0.40 < e < 0.55,0.01≤y≤0.13.
According to Li, Na, Ti, Co, Mn, Al, the mole of N and O takes lithia, sodium carbonate, titanium trichloride, nickel cobalt manganese, the sub-manganese of acetic acid and aluminium hydroxide, , mole is respectively: 2.5, 0.9, 3, 6.5, 5, 4.5 and 0.8, and add the lanthana of 2% of each component gross mass, enter to grind 10h in ball mill, then in the mixture obtained, add the sucrose accounting for its quality 10%, the carbon black of 5% and the acetone of 300%, form mixed liquor, and add NaOH regulate pH be 9, then mixture is adopted ball mill grinding 3-5h, by the mixture centrifugation obtained, and at 500 DEG C, process 10min by being separated the solids obtained, then at 800 DEG C, 1h is processed, then 950 DEG C of sintering 3-5h are heated to, naturally cooling obtains product.
This product is adopted to prepare lithium ion battery.

Claims (5)

1. a positive electrode for multicomponent material compound, is characterized in that, the chemical combination formula of described positive electrode is:
Li xna ati bco cmn dal en yo 4wherein 0.20≤x≤0.25,0.05 < a < 0.1,0.15 < b < 0.35,0.54 < c < 68,0.48 < d < 0.69,0.40 < e < 0.55,0.01≤y≤0.13.
2. the positive electrode of a kind of multicomponent material compound according to claim 1, it is characterized in that, the preparation method of described positive electrode is, according to Li, Na, Ti, Co, Mn, Al, the mole of N and O takes lithia, sodium carbonate, titanium trichloride, nickel cobalt manganese, the sub-manganese of acetic acid and aluminium hydroxide, and add the lanthana of 2% of each component gross mass, enter to grind 10-15h in ball mill, then in the mixture obtained, add the sucrose accounting for its quality 10%, the carbon black of 5% and the acetone of 300%, form mixed liquor, then mixture is adopted ball mill grinding 3-5h, by the mixture centrifugation obtained, and at 500 DEG C, process 10-30min by being separated the solids obtained, then at 800-850 DEG C, 1-2h is processed, then 900-950 DEG C of sintering 3-5h is heated to, naturally cooling obtains product.
3. the positive electrode of a kind of multicomponent material compound according to claim 2, is characterized in that, adds NaOH and regulate pH to be 8-9 in mixed liquor.
4. the positive electrode of a kind of multicomponent material compound according to claim 2, is characterized in that, separation is obtained solids and process 10min at 500 DEG C, then at 800 DEG C, process 1h, and be then heated to 950 DEG C of sintering 4h, cooling obtains product naturally.
5. a lithium ion battery, is characterized in that, described lithium ion battery adopts the positive electrode of a kind of multicomponent material compound according to claim 1 to be prepared from.
CN201410779893.4A 2014-12-17 2014-12-17 Multivariate material composite positive electrode and lithium ion battery Active CN104617262B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410779893.4A CN104617262B (en) 2014-12-17 2014-12-17 Multivariate material composite positive electrode and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410779893.4A CN104617262B (en) 2014-12-17 2014-12-17 Multivariate material composite positive electrode and lithium ion battery

Publications (2)

Publication Number Publication Date
CN104617262A true CN104617262A (en) 2015-05-13
CN104617262B CN104617262B (en) 2017-03-22

Family

ID=53151614

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410779893.4A Active CN104617262B (en) 2014-12-17 2014-12-17 Multivariate material composite positive electrode and lithium ion battery

Country Status (1)

Country Link
CN (1) CN104617262B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591531A (en) * 2017-09-25 2018-01-16 华南师范大学 A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application
CN114956198A (en) * 2021-02-24 2022-08-30 郭珺 P3 phase sodium manganese oxide material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800840A (en) * 2011-05-23 2012-11-28 中国科学院宁波材料技术与工程研究所 Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery
CN103456945A (en) * 2013-09-11 2013-12-18 山东齐星新材料科技有限公司 Preparation method of low-cost lithium ion battery anode material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800840A (en) * 2011-05-23 2012-11-28 中国科学院宁波材料技术与工程研究所 Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery
CN103456945A (en) * 2013-09-11 2013-12-18 山东齐星新材料科技有限公司 Preparation method of low-cost lithium ion battery anode material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591531A (en) * 2017-09-25 2018-01-16 华南师范大学 A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application
CN114956198A (en) * 2021-02-24 2022-08-30 郭珺 P3 phase sodium manganese oxide material and preparation method and application thereof
CN114956198B (en) * 2021-02-24 2024-02-27 郭珺 P3-phase sodium-manganese oxide material and preparation method and application thereof

Also Published As

Publication number Publication date
CN104617262B (en) 2017-03-22

Similar Documents

Publication Publication Date Title
WO2020063680A1 (en) Positive electrode active material and preparation method therefor, electrochemical cell, battery module, battery pack, and apparatus
CN104218234B (en) A kind of lithium ion battery composite cathode material of high circulation performance and preparation method thereof
CN101662025B (en) Lithium ion battery anode active material and preparing method thereof
CN102074692B (en) Preparation method for similar graphene doped lithium ion battery positive electrode material
CN106450282A (en) Large monocrystal lithium nickel manganate anode material and preparation method thereof
CN102694164B (en) Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material
JP4185191B2 (en) Method for producing spinel type lithium manganate
CN107492643A (en) A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof
CN103855389A (en) Ferric (III) fluoride / carbon composite material and its preparation method and application
CN105428637A (en) Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material
CN102034967A (en) Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery
CN104393234A (en) Modified lithium ion battery composite positive pole material and preparation method thereof
CN100505391C (en) honeycomb structure spherical LiFePO4 / C composite material preparation method
CN106784790A (en) A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material
CN103078100A (en) Lithium sodium manganate cathode material and preparation method thereof
CN102157753A (en) Fast-charging high-power winding column type lithium ion battery
CN110380043A (en) The positive electrode and preparation method thereof of fluoro- phosphorus doping tin oxide coating modification
CN110061225A (en) A kind of monocrystalline high capacity nickel-cobalt lithium manganate cathode material and preparation method thereof
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN111200166A (en) Method for modifying lithium metal interface of room-temperature solid-state battery
CN102280613B (en) Preparation method of lithium ion cell anode material coating carbon fiber and product thereof
KR20200032423A (en) Cathode material for sodium secondary batteries
CN102916180B (en) A kind of lithium ion battery preparation method of high-performance iron phosphate lithium composite
CN104617262B (en) Multivariate material composite positive electrode and lithium ion battery
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for 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
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 315800 standard workshop No. 2 of the 0212 massif in the West Zone of the Ningbo Free Trade Zone, Zhejiang

Patentee after: Ningbo Veken Battery Co., Ltd.

Address before: 315800 No. 5 West Avenue, Beilun Free Trade Zone, Ningbo, Zhejiang

Patentee before: Ningbo Veken Battery Co., Ltd.