CN102779993B - Lithium ion battery anode material and preparation method - Google Patents
Lithium ion battery anode material and preparation method Download PDFInfo
- Publication number
- CN102779993B CN102779993B CN201210272399.XA CN201210272399A CN102779993B CN 102779993 B CN102779993 B CN 102779993B CN 201210272399 A CN201210272399 A CN 201210272399A CN 102779993 B CN102779993 B CN 102779993B
- Authority
- CN
- China
- Prior art keywords
- lithium
- ball
- anode material
- ion battery
- lithium ion
- 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
-
- 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 lithium ion battery anode material and a preparation method, and belongs to the technical field of energy materials. The lithium ion battery anode material is mainly composed of a lithium ion battery anode material precursor and a lithium source. The lithium ion battery anode material is characterized by further comprising a flux which is niobium pentoxide or niobium hydroxide. The flux can effectively reduce the melting point of spinel lithium manganese oxide, melt surfaces of particles at a proper temperature, and remove corner angles of particles, so that the particles are made into a spherical-like shape; the surfaces of the particles have no corner angles and approximate a sphere shape, the specific surface area is large, and processability and structural stability of materials are greatly improved.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method, belong to technical field of energy material.
Background technology
Lithium ion battery has that voltage is high, memory-less effect, energy density are high and the feature such as cycle performance is good, and portable electronics is widely used.LiMn2O4 is one of more promising lithium ion anode material, compare traditional positive electrodes such as cobalt acid lithium, the advantages such as LiMn2O4 has aboundresources, cost is low, pollution-free, fail safe is good, good rate capability, be desirable power battery anode material, but its poor cycle performance and electrochemical stability greatly limit its industrialization.LiMn2O4 mainly comprises lithium manganate having spinel structure and layer structure LiMn2O4, wherein lithium manganate having spinel structure Stability Analysis of Structures, is easy to realize suitability for industrialized production, and existing market product is all this kind of structure.Lithium manganate having spinel structure belongs to cubic system, Fd3m space group, and theoretical specific capacity is 148mAh/g, owing to having three-dimensional tunnel structure, lithium ion can reversibly deintercalation from spinel crystal lattice, can not cause subsiding of structure, thus has excellent high rate performance and stability.
At present, tradition thinks that the shortcoming that LiMn2O4 energy density is low, cycle performance is poor has had very large change.Finishing and doping can effective its chemical properties of modification, and finishing can suppress dissolving and the electrolyte decomposition of manganese effectively.Doping effectively can suppress the Jahn-Teller effect in charge and discharge process.Finishing and doping are combined the chemical property that can improve material undoubtedly further, believes and can become one of the direction of from now on lithium manganate having spinel structure being carried out to study on the modification.
At present, have and spinel lithium manganate second particle done globulate, but its primary particle is sharp-featured, these corner angle add specific area, add the contact area of cell positive material and electrolyte, accelerate the reaction of cell positive material and electrolyte, thus reduce the stability of cell positive material; And these corner angle make cell positive material particle poor fluidity some, affect processing characteristics.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of anode material for lithium-ion batteries and preparation method are provided, this anode material for lithium-ion batteries exists with the form of individual particle, surface does not have corner angle subglobular, specific area is little, improves drawing abillity and structural stability greatly.
Technical scheme of the present invention is:
A kind of anode material for lithium-ion batteries, be mainly made up of precursor of lithium ionic cell positive material and lithium source, it is characterized in that also comprising flux, described flux is niobium pentaoxide or niobium hydroxide.
The positive electrode material precursor of described lithium ion battery is any one in electrolytic manganese dioxide, mangano-manganic oxide or manganous hydroxide.
Described lithium source is any one in lithium carbonate, lithium hydroxide or lithium oxalate.
The consumption of described precursor of lithium ionic cell positive material, lithium source and flux is according to Mn:Li:Nb=(1.74 ~ 1.995): (1 ~ 1.1): the mol ratio of (0.005 ~ 0.01) calculates.
This kind of anode material for lithium-ion batteries also can comprise doped source compound, and described doped source compound is any one in the oxide/hydroxide of aluminium, chromium or nickel, and described doped source compound amount accounts for 0 ~ 3.0% of system total weight.
A preparation method for anode material for lithium-ion batteries, comprises the steps:
Raw material for standby is taken by above-mentioned mol ratio;
(1), by manganese source, lithium source and flux ball milling 2 ~ 5 hours in ball mill, it is 2 ~ 12 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, heat with the programming rate of 1 ~ 20 DEG C/min under air atmosphere, to 600 ~ 780 DEG C of insulation 6 ~ 12h, continue to be warming up to 800 ~ 1000 DEG C of insulation 6 ~ 12h, with stove cooling, obtain caking material;
(3), pulverize in pulverizer after material to be sintered cooling, being crushed to median diameter is 5 ~ 20 μm, mixes after this agglutinating matter and be incubated 6 ~ 12h at 600 ~ 800 DEG C, obtain individual particle class spherical lithium manganate target product.
Above-mentioned steps also can add doped source compound in (1), and described doped source compound is any one in the oxide/hydroxide of aluminium, chromium or nickel, and described doped source compound amount accounts for 0 ~ 3.0% of system total weight.
Zirconium ball is adopted to be ball-milling medium in described ball mill.
Anode material for lithium-ion batteries of the present invention is spinelle manganic acid lithium material.
The present invention is fluxed by flux and reaches the finishing of anode material for lithium-ion batteries, the effect that wherein flux plays is: the fusing point significantly reducing spinel lithium manganate, at a suitable temperature, accomplishes that particle surface melts, remove the corner angle of particle, particle is made class spherical.
The invention has the beneficial effects as follows:
Anode material for lithium-ion batteries exists with the form of individual particle, and surface does not have corner angle subglobular, and thus the specific area of material is very little, has following advantage:
(1), raw material is easy to get, and cost is low;
(2), technique is simple, and do not introduce complicated process engineering, thus cost of manufacture is low;
(3), particle is individual particle, smooth surface, and specific area is very little;
(4), good fluidity, be easy to processing;
(5), material void rate is low, and thus compacting is very high, can reach 3.5g/cm
3;
(6), make battery after, the contact area of material and electrolyte is very little, reduces the contact area of material and electrolyte, reduces the reaction of material and electrolyte, thus adds the stability of material, improves cycle performance and the high-temperature behavior of material.
Accompanying drawing explanation
Fig. 1 is the SEM collection of illustrative plates of the anode material for lithium-ion batteries by embodiment 1 preparation;
Fig. 2 is the SEM collection of illustrative plates of the anode material for lithium-ion batteries by embodiment 2 preparation;
Fig. 3 is the SEM collection of illustrative plates of the anode material for lithium-ion batteries by embodiment 3 preparation;
Fig. 4 is the SEM collection of illustrative plates of the anode material for lithium-ion batteries by embodiment 4 preparation;
Fig. 5 is the SEM collection of illustrative plates of the anode material for lithium-ion batteries prepared by comparative example;
Embodiment
Embodiment 1
(1), by 200kg mangano-manganic oxide, 51.46kg battery-level lithium carbonate, 0.88kg niobium pentaoxide ball milling 3 hours in ball mill, ball-milling medium adopts zirconium ball, is 5 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 2 DEG C/min under air atmosphere, to 700 DEG C of insulation 10h, continue to be warming up to 900 DEG C of insulation 10h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 12 ~ 15 μm, is incubated 8h after mixing this agglutinating matter at 750 DEG C, obtains individual particle class spherical lithium manganate target product.
Embodiment 2
(1), by 200kg mangano-manganic oxide, 55.49kg battery-level lithium carbonate (Li
2cO
3), 1.81kg niobium pentaoxide (Nb
2o
5) ball milling 4 hours in ball mill, ball-milling medium adopts zirconium ball, is 3 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 8 DEG C/min under air atmosphere, to 650 DEG C of insulation 8h, continue to be warming up to 850 DEG C of insulation 12h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 4 ~ 6 μm, is incubated 10h after mixing this agglutinating matter at 650 DEG C, obtains individual particle class spherical lithium manganate target product.
Embodiment 3
(1), by 200kg mangano-manganic oxide, 56.26kg battery-level lithium carbonate (Li
2cO
3), 1.87kg niobium pentaoxide (Nb
2o
5) and 8.79kg aluminium hydroxide (Al (OH)
3) ball milling 2 hours in ball mill, ball-milling medium adopts zirconium ball, is 10 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 15 DEG C/min under air atmosphere, to 750 DEG C of insulation 7h, continue to be warming up to 950 DEG C of insulation 7h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 6 ~ 8 μm, is incubated 8h after mixing this agglutinating matter at 750 DEG C, obtains individual particle class spherical lithium manganate target product.
Embodiment 4
(1), by 228kg electrolytic manganese dioxide (EMD), 36.18kg lithium hydroxide (LiOH), 3.64kg niobium pentaoxide (Nb
2o
5) ball milling 2.5 hours in ball mill, ball-milling medium adopts zirconium ball, is 8 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 5 DEG C/min under air atmosphere, to 600 DEG C of insulation 12h, continue to be warming up to 950 DEG C of insulation 7h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 8 ~ 12 μm, is incubated 12h after mixing this agglutinating matter at 600 DEG C, obtains individual particle class spherical lithium manganate target product.
Comparative example
(1), by 200kg mangano-manganic oxide and 51.46kg battery-level lithium carbonate ball milling 3 hours in ball mill, ball-milling medium adopts zirconium ball, is 5 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 2 DEG C/min under air atmosphere, to 700 DEG C of insulation 10h, continue to be warming up to 850 DEG C of insulation 12h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 12 ~ 15 μm, is incubated 8h after mixing this agglutinating matter at 750 DEG C, obtains individual particle class spherical lithium manganate target product.
The SEM collection of illustrative plates of the anode material for lithium-ion batteries prepared by embodiment 1-4 can be found out, material surface does not have corner angle subglobular, and specific area is little; The SEM collection of illustrative plates of anode material for lithium-ion batteries prepared by comparative example can be found out, material surface corner angle are clearly demarcated, and therefore the present invention is successfully fluxed by flux and reaches the finishing of anode material for lithium-ion batteries.
Claims (1)
1. an anode material for lithium-ion batteries, be mainly made up of precursor of lithium ionic cell positive material and lithium source, it is characterized in that, preparation process is as follows:
(1), by 200kg mangano-manganic oxide, 51.46kg battery-level lithium carbonate, 0.88kg niobium pentaoxide ball milling 3 hours in ball mill, ball-milling medium adopts zirconium ball, is 5 μm to ball average grit diameter;
(2), gained ball milling material is put in saggar, sinters in roller kilns, with the heating of the programming rate of 2 DEG C/min under air atmosphere, to 700 DEG C of insulation 10 h, continue to be warming up to 900 DEG C of insulation 10h, with stove cooling, obtain caking material;
(3), material to be sintered cooling after pulverize in pulverizer, being crushed to median diameter is 12 ~ 15 μm, is incubated 8 h after mixing this agglutinating matter at 750 DEG C, obtains individual particle class spherical lithium manganate target product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210272399.XA CN102779993B (en) | 2012-07-31 | 2012-07-31 | Lithium ion battery anode material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210272399.XA CN102779993B (en) | 2012-07-31 | 2012-07-31 | Lithium ion battery anode material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102779993A CN102779993A (en) | 2012-11-14 |
| CN102779993B true CN102779993B (en) | 2015-04-08 |
Family
ID=47124831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210272399.XA Active CN102779993B (en) | 2012-07-31 | 2012-07-31 | Lithium ion battery anode material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102779993B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103560287A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as robot power source |
| CN103560294A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as weeding machine power source |
| CN103560289A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as unmanned plane power source |
| CN103560284A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of battery pack consisting of zero power supply and lithium ion battery as power supply of automobile tire pressure sensor |
| CN103560298A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as disabled electromobile power source |
| CN103560290A (en) * | 2013-11-05 | 2014-02-05 | 沈晓斌 | Application of zero power source-lithium ion battery battery pack as airship power source |
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN106629858A (en) * | 2016-10-10 | 2017-05-10 | 北京化工大学 | Method for removing fine powder in lithium manganate electrode materials in situ |
| CN112993236A (en) * | 2019-12-18 | 2021-06-18 | 天津国安盟固利新材料科技股份有限公司 | Single-particle lithium manganate cathode material and preparation method thereof |
| CN114613985A (en) * | 2022-03-07 | 2022-06-10 | 宁波容百新能源科技股份有限公司 | High-voltage nickel-manganese material with high single crystal dispersibility as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540399A (en) * | 2009-04-24 | 2009-09-23 | 济宁市无界科技有限公司 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
| CN101908614A (en) * | 2009-11-10 | 2010-12-08 | 高要市凯思特电池材料有限公司 | High-density lithium manganate anode material and preparation method thereof |
-
2012
- 2012-07-31 CN CN201210272399.XA patent/CN102779993B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540399A (en) * | 2009-04-24 | 2009-09-23 | 济宁市无界科技有限公司 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
| CN101908614A (en) * | 2009-11-10 | 2010-12-08 | 高要市凯思特电池材料有限公司 | High-density lithium manganate anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102779993A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102779993B (en) | Lithium ion battery anode material and preparation method | |
| CN1332878C (en) | Prepn process of oxygen place doped lithium ferric phosphate powder | |
| CN100470894C (en) | Preparation method of phosphorus position partly substituted iron lithium phosphate powder | |
| KR101895641B1 (en) | Cathode material and lithium ion battery therefrom | |
| CN101955175B (en) | Industrial preparation method for lithium iron phosphate | |
| CN106159244A (en) | Lithium battery cathode material, preparation method thereof and lithium ion battery for power | |
| CN103872315B (en) | A kind of preparation method of cobalt acid lithium composite positive pole of Ge-doped high-energy-density | |
| CN102201573A (en) | Rich-lithium positive electrode material of lithium ion battery having coreshell structure and preparation method of rich-lithium positive electrode material | |
| CN103682318A (en) | Preparation method for high safety nickel cobalt manganese acid lithium NCM 523 ternary material | |
| CN102403505B (en) | Method for preparing in-situ carbon coated lithium manganese borate composite material by lithium ion battery cathode material | |
| CN104201366A (en) | Preparing method of high-safety high-compacted-density nickel cobalt lithium manganate NCM523 ternary material | |
| CN106450289A (en) | High-voltage lithium cobalt oxide positive electrode material and preparation method therefor | |
| CN103474646B (en) | A kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN102832387B (en) | Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application thereof | |
| CN103682292B (en) | The lithium titanate material preparation method of high-tap density | |
| CN112537804B (en) | Lithium-doped high-entropy oxide battery negative electrode material and preparation and application methods thereof | |
| CN102263263A (en) | Zinc and fluorine doped carbon coating lithium manganese phosphate positive electrode material and preparation method thereof | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN102723494A (en) | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof | |
| CN104037412A (en) | Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery | |
| CN101908614B (en) | High-density lithium manganate anode material and preparation method thereof | |
| CN103050698A (en) | Vanadium lithium iron phosphate anode material and preparation method thereof | |
| CN102447097A (en) | Preparation method of lithium ion cathode material nickel manganese cobalt | |
| CN103693632B (en) | A kind of preparation method of lithium vanadyl phosphate positive 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 | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 276025 No. 119, Yanan Road, Linyi Economic Development Zone, Shandong, China Patentee after: Shandong Tianjiao new energy Co. Ltd. Address before: 276025 No. 119, Yanan Road, Linyi Economic Development Zone, Shandong, China Patentee before: Linyi Gelon Battery Material Co., Ltd. |