CN106299336B - The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode - Google Patents
The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode Download PDFInfo
- Publication number
- CN106299336B CN106299336B CN201510393225.2A CN201510393225A CN106299336B CN 106299336 B CN106299336 B CN 106299336B CN 201510393225 A CN201510393225 A CN 201510393225A CN 106299336 B CN106299336 B CN 106299336B
- Authority
- CN
- China
- Prior art keywords
- hollow
- positive electrode
- lithium
- predecessor
- shape micro
- 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.)
- Active
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
- H01M4/48—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation methods of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode, since the material has hollow bipyramid shape micro-nano structure, it is still able to maintain preferable crystallinity and microscopic appearance with high specific discharge capacity and excellent high temperature cyclic performance after it experienced prolonged charge-discharge cycle.The preparation method has many advantages, such as that raw material is cheap and easy to get, easy to operation, green economy is environmentally friendly, is advantageously implemented large-scale industrialized production.
Description
Technical field
The present invention relates to the technology of lithium ion secondary battery anode material, specifically a kind of hollow bipyramid shape micro-nano
The preparation method of structure lithium manganate having spinel structure positive electrode.
Background technique
Positive electrode is the key raw material of lithium ion battery, and the quality of performance determines the performance of lithium ion battery,
The height of its price determines the cost of lithium ion battery.In addition, although the research of lithium ion battery achieves very greatly in recent years
Development, especially in terms of negative electrode material system and electrolyte system, but for positive electrode, development relatively lags behind.Therefore,
The positive electrode for studying lithium ion battery has vital meaning for developing and improving the performance of entire battery.At present
Positive electrode in the market is based on cobalt acid lithium, lithium nickel cobalt dioxide, LiFePO 4, nickle cobalt lithium manganate, lithium manganate having spinel structure etc.
Material has also occupied certain market share.Cobalt acid lithium is the positive electrode for taking the lead in realizing merchandized handling, prepares simple, property
It can stablize, technical maturity, but cobalt is a kind of global strategic resource and toxic, these all limit lithium cobaltate cathode
The further development of material.
In numerous anode material for lithium-ion batteries, spinelle LiMn2O4Since promoter manganese is abundant, cheap, environment
Friendly, the advantages that platform voltage is high, in lithium ion battery, especially in electric car (EV) and hybrid vehicle (HEV) electricity
In pond using great competition potential, become by researcher pay close attention to object.Spinelle LiMn2O4In nineteen eighty-three for the first time by
Thackeray M. M. et al. is used for lithium ion battery as positive electrode.The material category cubic system, Fd3m space group, reason
It is 148 mAh/g by capacity, discharge platform is in 4V or so.Since there are Mn in electrochemistry circulation for the material3+Jahn-
Teller effect, Mn dissolve in the electrolytic solution and the factors such as decomposition of the electrolyte under high potential, leads to LiMn2O4Capacity
Decay, is showed under high temperature (50 DEG C) particularly evident.These all limit spinel-type LiMn2O4The extensive hair of material
Exhibition.For these problems, the measure mainly taken at present is doping anions and canons and surface cladding inert substance etc., by right
Jahn-Teller effect inhibits and reduces the contact area of active material and electrolyte effectively to slow down the dissolution of Mn, thus
Improve LiMn2O4Chemical property.In addition, the chemical property of material is also influenced by preparation method.Traditional is direct
Though high temperature solid-state method have many advantages, such as it is easy to operate, be easy to produce in enormous quantities, the lithium manganate material grain prepared in this way
It is not easy to control to spend size, performance batch less stable, and energy consumption is very big.Therefore, exploring optimal preparation method is also spinelle
LiMn2O4One of research direction.Though in conclusion the research of current lithium manganate having spinel structure positive electrode obtained it is larger
Progress, but its performance need to be improved, to meet industrial demand.Therefore there is an urgent need to change to its performance
Into the structure of material being improved especially from preparation method, to make it have more excellent chemical property, with real as early as possible
Existing industrialized production.
Summary of the invention
It is an object of the present invention to provide a kind of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure LiAl0.1Mn1.9O4System
Preparation Method.
Technical program of the present invention lies in:
Steps are as follows:
(1) by KMnO4It is dissolved in deionized water, appropriate hydrochloric acid is added, is made into KMnO4Concentration is 0.01~0.02mol/L,
Concentration of hydrochloric acid is the solution of 0.5~0.8mol/L；
(2) above-mentioned mixed solution after mixing evenly, is pumped into hydrothermal reaction kettle, before 120~170 DEG C of reactions generate
Drive object β-MnO2；
(3) after predecessor being filtered, washed, being dried with lithium compound, aluminum nitrate Li:Al:Mn=1:0.1 in molar ratio:
1.9 ratio is uniformly mixed, and drying is carried out between 80~120 DEG C；
(4) by the homogeneous mixture of predecessor and lithium compound in tube furnace under 700~800 DEG C of high temperature fire 10~
20h obtains LiAl after being down to room temperature0.1Mn1.9O4Material.
In above-mentioned technical proposal: the mixed solution being added in reaction kettle in step (2) account for reaction kettle total measurement (volume) 50~
80%, the reaction time is 14~20h.
Be filtered, washed described in step (3) is the K so that in predecessor+Total content is less than 300ppm, Cl-Total content is small
In 0.5%.
Lithiumation object can be lithium hydroxide or lithium carbonate in step (3).
High temperature described in step (4) is fired, and heating rate is 5~10 DEG C/min, then again with the drop of 1~5 DEG C/min
Warm rate is to room temperature.
The beneficial effects of the present invention are:
1, specific capacity is high.Using the lithium ion battery specific capacity height that material of the present invention makes as positive electrode, 3.5
With 0.5 C(1 C=148mA h/g between~4.3V) rate charge-discharge when, specific discharge capacity can reach 125mA h/g.This master
If not only having shortened the diffusion path of lithium ion, but also improve activity since the material synthesized with the method is hollow micro-nano structure
The abundant wellability of material and electrolyte, to improve its specific discharge capacity.
2, high temperature cyclic performance is stablized.The lithium ion battery made using material of the present invention as positive electrode is 3.5
After being recycled 500 weeks under 50 DEG C of high temperature with 3 C between~4.3V, capacity is still able to maintain 70% or more.This is mainly due to
The method synthesis material be hollow structure, can alleviate in charge and discharge cycles due to lithium it is embedding/take off caused by volume expansion/receipts
Contracting, to enhance the structural stability of material.
3, environment-friendly material.Material of the present invention is substantially free of noxious material, is a kind of environment friendly material.
4, at low cost.Material of the present invention is based on resource manganese abundant, therefore cost is very low, superiority of effectiveness
Clearly.
5, preparation method is simple.Material preparation method provided by the invention is simple and easy to do, raw material is cheap and easy to get, nontoxic
It is harmless, it is good for the environment type industrialized development.
Detailed description of the invention
Fig. 1 is LiAl of the present invention0.1Mn1.9O4The TEM of material schemes.
Fig. 2 is LiAl of the present invention0.1Mn1.9O4The XRD diagram of material.
Fig. 3 is LiAl of the present invention0.1Mn1.9O4The high temperature circulation curve (3.5-4.3V, 3C) of material.
Specific embodiment
Embodiment 1
Steps are as follows:
(1) by KMnO4It is dissolved in deionized water, appropriate hydrochloric acid is added, is made into KMnO4Concentration is 0.01mol/L, and hydrochloric acid is dense
Degree is the solution of 0.5mol/L；
(2) above-mentioned mixed solution after mixing evenly, is pumped into hydrothermal reaction kettle, generates predecessor β-in 120 DEG C of reactions
MnO2；
(3) after predecessor being filtered, washed, being dried with lithium compound, aluminum nitrate Li:Al:Mn=1:0.1 in molar ratio:
1.9 ratio is uniformly mixed, and drying is carried out at 80 DEG C；
(4) homogeneous mixture of predecessor and lithium compound is fired into 10h under 700 DEG C of high temperature in tube furnace, be down to often
LiAl is obtained after temperature0.1Mn1.9O4Material.
The mixed solution being added in reaction kettle in step (2) accounts for the 50% of reaction kettle total measurement (volume), reaction time 14h.
Be filtered, washed described in step (3) is the K so that in predecessor+Total content is less than 300ppm, Cl-Total content is small
In 0.5%.
Lithium compound can be lithium hydroxide or lithium carbonate in step (3).
High temperature described in step (4) fire, heating rate is 5 DEG C/min, then again with the rate of temperature fall of 1 DEG C/min extremely
Room temperature.
Embodiment 2
Steps are as follows:
(1) by KMnO4It is dissolved in deionized water, appropriate hydrochloric acid is added, is made into KMnO4Concentration is 0.015mol/L, hydrochloric acid
Concentration is the solution of 0.7mol/L；
(2) above-mentioned mixed solution after mixing evenly, is pumped into hydrothermal reaction kettle, generates predecessor β-in 150 DEG C of reactions
MnO2；
(3) after predecessor being filtered, washed, being dried with lithium compound, aluminum nitrate Li:Al:Mn=1:0.1 in molar ratio:
1.9 ratio is uniformly mixed, and drying is carried out at 100 DEG C；
(4) homogeneous mixture of predecessor and lithium compound is fired into 15h under 750 DEG C of high temperature in tube furnace, be down to often
It obtains after temperature up to LiAl is arrived0.1Mn1.9O4Material.
The mixed solution being added in reaction kettle in step (2) accounts for the 70% of reaction kettle total measurement (volume), reaction time 17h.
Be filtered, washed described in step (3) is the K so that in predecessor+Total content is less than 300ppm, Cl-Total content is small
In 0.5%.
Lithium compound can be lithium hydroxide or lithium carbonate in step (3).
High temperature described in step (4) fire, heating rate is 8 DEG C/min, then again with the rate of temperature fall of 3 DEG C/min extremely
Room temperature.
Embodiment 3
Steps are as follows:
(1) by KMnO4It is dissolved in deionized water, appropriate hydrochloric acid is added, is made into KMnO4Concentration is 0.02mol/L, and hydrochloric acid is dense
Degree is the solution of 0.8mol/L；
(2) above-mentioned mixed solution after mixing evenly, is pumped into hydrothermal reaction kettle, generates predecessor β-in 170 DEG C of reactions
MnO2；
(3) after predecessor being filtered, washed, being dried with lithium compound, aluminum nitrate Li:Al:Mn=1:0.1 in molar ratio:
1.9 ratio is uniformly mixed, and drying is carried out at 120 DEG C；
(4) homogeneous mixture of predecessor and lithium compound is fired to 20h in tube furnace to get arriving under 800 DEG C of high temperature
LiAl0.1Mn1.9O4Material.
The mixed solution being added in reaction kettle in step (2) accounts for the 80% of reaction kettle total measurement (volume), reaction time 20h.
Be filtered, washed described in step (3) is the K so that in predecessor+Total content is less than 300ppm, Cl-Total content is small
In 0.5%.
Lithium compound can be lithium hydroxide or lithium carbonate in step (3).
High temperature described in step (4) is fired, and heating rate is 10 DEG C/min, then again with the rate of temperature fall of 5 DEG C/min
To room temperature.
Claims (4)
1. a kind of preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode, it is characterised in that:
The following steps are included:
(1) by KMnO4It is dissolved in deionized water, appropriate hydrochloric acid is added, is made into KMnO4Concentration is 0.01 ~ 0.02mol/L, hydrochloric acid
Concentration is the solution of 0.5 ~ 0.8mol/L；
(2) above-mentioned mixed solution after mixing evenly, is pumped into hydrothermal reaction kettle, generates predecessor β-in 120-170 DEG C of reaction
MnO2；
(3) predecessor is filtered, washed, so that the K in predecessor+Total content is less than 300ppm, Cl-Total content is less than 0.5%；It will
It is uniformly mixed after predecessor drying with the ratio of lithium compound, aluminum nitrate Li:Al:Mn=1:0.1:1.9 in molar ratio, drying is
It is carried out between 80-120 DEG C；
(4) by the homogeneous mixture of predecessor and lithium compound in tube furnace under 700 ~ 800 DEG C of high temperature fire 10 ~ 20h to get
To LiAl0.1Mn1.9O4Material.
2. a kind of preparation side of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode according to claim 1
Method, it is characterised in that: the mixed solution being added in reaction kettle in step (2) accounts for the 50 ~ 80% of reaction kettle total measurement (volume), when reaction
Between be 14-20h.
3. a kind of preparation side of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode according to claim 1
Method, it is characterised in that: lithium compound is lithium hydroxide or lithium carbonate in step (3).
4. a kind of preparation side of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode according to claim 1
Method, it is characterised in that: high temperature described in step (4) is fired, and heating rate is 5 ~ 10 DEG C/min, then again with 1 ~ 5 DEG C/min
Rate of temperature fall to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510393225.2A CN106299336B (en) | 2015-07-07 | 2015-07-07 | The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510393225.2A CN106299336B (en) | 2015-07-07 | 2015-07-07 | The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106299336A CN106299336A (en) | 2017-01-04 |
| CN106299336B true CN106299336B (en) | 2019-02-01 |
Family
ID=57650312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510393225.2A Active CN106299336B (en) | 2015-07-07 | 2015-07-07 | The preparation method of hollow bipyramid shape micro-nano structure lithium manganate having spinel structure positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106299336B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108649217B (en) * | 2018-05-09 | 2021-09-28 | 哈尔滨工业大学（威海） | Preparation method of high-voltage lithium battery anode material bat mixed lithium nickel manganese oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710735A (en) * | 2005-07-15 | 2005-12-21 | 广州鸿森材料有限公司 | Method for synthesizing lithium ion cell positive cell polar material rotary furnace |
| CN101764223A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof |
| CN101780983A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery |
| CN103880088A (en) * | 2014-02-28 | 2014-06-25 | 段晶晶 | Preparation method and catalytic application of hollow dual-cone beta-MnO2 |
-
2015
- 2015-07-07 CN CN201510393225.2A patent/CN106299336B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710735A (en) * | 2005-07-15 | 2005-12-21 | 广州鸿森材料有限公司 | Method for synthesizing lithium ion cell positive cell polar material rotary furnace |
| CN101780983A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery |
| CN101764223A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof |
| CN103880088A (en) * | 2014-02-28 | 2014-06-25 | 段晶晶 | Preparation method and catalytic application of hollow dual-cone beta-MnO2 |
Non-Patent Citations (1)
| Title |
|---|
| "微纳结构LiMn2O4的可控合成及其电化学性能研究";丁元力;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20111115(第11期);第35、52-55页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106299336A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104157831B (en) | Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof | |
| CN110002465A (en) | A kind of white analog positive electrode in Prussia, preparation method and application | |
| CN104393285B (en) | Nickel-cobalt-aluminum ternary positive electrode material and its preparation method | |
| CN104037404B (en) | A kind of lithium ion battery nickel cobalt aluminum lithium and LiMn2O4 composite and preparation method thereof | |
| CN103762353B (en) | A kind of heterogeneous nucleocapsid structure high-capacity lithium ion battery electricity positive electrode with and preparation method thereof | |
| CN105990577B (en) | A kind of anode material for lithium-ion batteries LiNi0.6-xCo0.2Mn0.2AlxO2-yFyAnd preparation method thereof | |
| CN102569781B (en) | High-voltage lithium ion battery cathode material and preparation method thereof | |
| CN103972499B (en) | A kind of nickel cobalt lithium aluminate cathode material of modification and preparation method thereof | |
| CN104112845B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN103855387A (en) | Modified lithium ion battery ternary positive electrode material and preparation method thereof | |
| CN103855384A (en) | Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof | |
| CN103117380A (en) | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery | |
| CN104966820A (en) | Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof | |
| CN103794752A (en) | High voltage nickel lithium manganate cathode materials with core-shell structure and preparation method thereof | |
| CN108550791A (en) | A kind of layered cathode material and its preparation method and application of spinelle cladding | |
| CN106058203A (en) | Preparation method of double-covering lithium-enriched manganese-based material using zirconium phosphate as outer covering and calcium fluoride as inner covering | |
| CN102723495A (en) | High-voltage lithium ion battery cathode material of copper-doped lithium manganate and preparation method thereof | |
| CN103606673A (en) | Preparation method of laminar-spinel compound sosoloid anode material | |
| CN109088067A (en) | A kind of preparation method of low cobalt doped spinel-layer structure nickel ion doped two-phase composite positive pole | |
| CN105355907A (en) | Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application | |
| CN104779383A (en) | Preparation method of high-specific-energy cathode material of lithium ion battery | |
| CN107611384A (en) | A kind of high-performance concentration gradient high-nickel material, its preparation method and the purposes in lithium ion battery | |
| CN104051725A (en) | Preparation method for high-voltage nickel-cobalt-manganese-lithium oxide positive electrode material | |
| CN103746113A (en) | Preparation method of coated spinel lithium manganate composite cathode material | |
| CN104051709A (en) | Preparation method of lithium ion battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190515 Address after: 554300 Northern Industrial Park, Dalong Economic Development Zone, Tongren, Guizhou Patentee after: Guizhou best new energy materials Co., Ltd. Address before: 441053 Scientific Research Department, Hubei Academy of Arts and Sciences, 296 Longzhong Road, Xiangcheng District, Xiangfan City, Hubei Province Patentee before: Hubei University of Arts and Science |
|
| TR01 | Transfer of patent right |