CN102779993A - Lithium ion battery anode material and preparation method - Google Patents
Lithium ion battery anode material and preparation method Download PDFInfo
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- CN102779993A CN102779993A CN201210272399XA CN201210272399A CN102779993A CN 102779993 A CN102779993 A CN 102779993A CN 201210272399X A CN201210272399X A CN 201210272399XA CN 201210272399 A CN201210272399 A CN 201210272399A CN 102779993 A CN102779993 A CN 102779993A
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- 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
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- 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 the energy and material technical field.
Background technology
Lithium ion battery has characteristics such as voltage height, memory-less effect, energy density height and cycle performance are good, on portable electronics, has obtained using widely.LiMn2O4 is one of more promising lithium ion anode material; Traditional positive electrodes such as treatment acid lithium; 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 relatively poor cycle performance and the big limitations of electrochemical stability its industrialization.LiMn2O4 mainly comprises lithium manganate having spinel structure and layer structure LiMn2O4, and wherein the lithium manganate having spinel structure Stability Analysis of Structures is easy to realize suitability for industrialized production, and the existing market product all is this kind structure.Lithium manganate having spinel structure belongs to cubic system, and Fd3m space group, theoretical specific capacity are 148mAh/g; Owing to have the three-dimensional tunnel structure; Lithium ion can take off embedding reversiblely from the spinelle lattice, can not cause subsiding of structure, thereby has excellent high rate performance and stability.
At present, tradition thinks that the LiMn2O4 energy density is low, the shortcoming of cycle performance difference has had very big change.The finishing and effectively its chemical property of modification that mixes, finishing can suppress the dissolving and the electrolyte decomposition of manganese effectively.Doping can effectively suppress the Jahn-Teller effect in the charge and discharge process.With finishing and mix and to combine can further improve undoubtedly the chemical property of material, believing to become one of direction of from now on lithium manganate having spinel structure being carried out study on the modification.
At present; Have the spinel lithium manganate second particle is done globulate; But its primary particle is sharp-featured, and these corner angle have increased specific area, has increased the contact area of cell positive material and electrolyte; Quicken the reaction of cell positive material and electrolyte, thereby reduced the stability of cell positive material; And these corner angle make the mobile weaker of cell positive material particle, influence processing characteristics.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A kind of anode material for lithium-ion batteries and preparation method are provided; This anode material for lithium-ion batteries is that the form with individual particle exists; The surface does not have the corner angle subglobular, and specific area is little, has improved drawing abillity and structural stability greatly.
Technical scheme of the present invention is:
A kind of anode material for lithium-ion batteries mainly is to be processed by precursor of lithium ionic cell positive material and lithium source, it is characterized in that also comprising flux, and said flux is niobium pentaoxide or niobium hydroxide.
The positive electrode presoma of said lithium ion battery is any one in electrolytic manganese dioxide, mangano-manganic oxide or the manganous hydroxide.
Said lithium source is any one in lithium carbonate, lithium hydroxide or the lithium oxalate.
The consumption of said 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) is calculated.
This kind anode material for lithium-ion batteries also can comprise the doped source compound, any one in the oxide/hydroxide that said doped source compound is aluminium, chromium or nickel, and said doped source compound amount accounts for 0～3.0% of system total weight.
A kind of preparation method of anode material for lithium-ion batteries comprises the steps:
Take by weighing raw material for standby by above-mentioned mol ratio;
(1), with manganese source, lithium source and flux ball milling 2～5 hours in ball mill, to ball milling material average grain diameter be 2～12 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns, under air atmosphere with the programming rate heating of 1～20 ℃/min; To 600～780 ℃ of insulation 6～12h; Continue to be warming up to 800～1000 ℃ of insulation 6～12h,, obtain the caking material with the stove cooling;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 5～20 μ m, at 600～800 ℃ of insulation 6～12h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
Above-mentioned steps also can add the doped source compound in (1), any one in the oxide/hydroxide that said doped source compound is aluminium, chromium or nickel, and said doped source compound amount accounts for 0～3.0% of system total weight.
Adopting the zirconium ball in the said ball mill is ball-milling medium.
Anode material for lithium-ion batteries of the present invention is spinelle manganic acid lithium material.
The present invention fluxes through flux and reaches the finishing of anode material for lithium-ion batteries; Wherein the effect played of flux is: reduced the fusing point of spinel lithium manganate effectively, under suitable temperature, accomplished the particle surface fusing; Remove the corner angle of particle, particle type of making is spherical.
The invention has the beneficial effects as follows:
Anode material for lithium-ion batteries is that the form with individual particle exists, and the surface does not have the corner angle subglobular, thereby the specific area of material is very little, has following advantage:
(1), raw material is easy to get, cost is low;
(2), technology is simple, introduce complicated process engineering, thereby cost of manufacture is low;
(3), particle is individual particle, smooth surface, specific area is very little;
(4), good fluidity, be easy to processing;
(5), the material void rate is low, thereby compacting is very high, can reach 3.5g/cm
3
(6), make battery after, the contact area of material and electrolyte is very little, has reduced the contact area of material and electrolyte, has reduced the reaction of material and electrolyte, thereby has increased the stability of material, has improved the cycle performance and the high-temperature behavior of material.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates by the anode material for lithium-ion batteries of embodiment 1 preparation;
Fig. 2 is the SEM collection of illustrative plates by the anode material for lithium-ion batteries of embodiment 2 preparations;
Fig. 3 is the SEM collection of illustrative plates by the anode material for lithium-ion batteries of embodiment 3 preparations;
Fig. 4 is the SEM collection of illustrative plates by the anode material for lithium-ion batteries of embodiment 4 preparations;
Fig. 5 is the SEM collection of illustrative plates by the anode material for lithium-ion batteries of Comparative Examples preparation;
Embodiment
(1), with 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 the zirconium ball, to ball milling material average grain diameter be 5 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns with the programming rate heating of 2 ℃/min, to 700 ℃ of insulation 10h, continues to be warming up to 900 ℃ of insulation 10h under air atmosphere, with the stove cooling, obtain the caking material;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 12～15 μ m, at 750 ℃ of insulation 8h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
Embodiment 2
(1), with 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 the zirconium ball, to ball milling material average grain diameter be 3 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns with the programming rate heating of 8 ℃/min, to 650 ℃ of insulation 8h, continues to be warming up to 850 ℃ of insulation 12h under air atmosphere, with the stove cooling, obtain the caking material;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 4～6 μ m, at 650 ℃ of insulation 10h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
Embodiment 3
(1), with 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 the zirconium ball, to ball milling material average grain diameter be 10 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns with the programming rate heating of 15 ℃/min, to 750 ℃ of insulation 7h, continues to be warming up to 950 ℃ of insulation 7h under air atmosphere, with the stove cooling, obtain the caking material;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 6～8 μ m, at 750 ℃ of insulation 8h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
Embodiment 4
(1), with 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 the zirconium ball, to ball milling material average grain diameter be 8 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns with the programming rate heating of 5 ℃/min, to 600 ℃ of insulation 12h, continues to be warming up to 950 ℃ of insulation 7h under air atmosphere, with the stove cooling, obtain the caking material;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 8～12 μ m, at 600 ℃ of insulation 12h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
Comparative Examples
(1), with 200kg mangano-manganic oxide and 51.46kg battery-level lithium carbonate ball milling 3 hours in ball mill, ball-milling medium adopts the zirconium ball, to ball milling material average grain diameter be 5 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns with the programming rate heating of 2 ℃/min, to 700 ℃ of insulation 10h, continues to be warming up to 850 ℃ of insulation 12h under air atmosphere, with the stove cooling, obtain the caking material;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 12～15 μ m, at 750 ℃ of insulation 8h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
SEM collection of illustrative plates according to the prepared anode material for lithium-ion batteries of embodiment 1-4 can find out that material surface does not have the corner angle subglobular, and specific area is little; The SEM collection of illustrative plates of the anode material for lithium-ion batteries of Comparative Examples preparation can find out that the material surface corner angle are clearly demarcated, so the flux that passes through of the present invention's success is fluxed and reached the finishing of anode material for lithium-ion batteries.
Claims (8)
1. an anode material for lithium-ion batteries mainly is to be processed by precursor of lithium ionic cell positive material and lithium source, it is characterized in that also comprising flux, and said flux is niobium pentaoxide or niobium hydroxide.
2. a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that: the positive electrode presoma of said lithium ion battery is any one in electrolytic manganese dioxide, mangano-manganic oxide or the manganous hydroxide.
3. a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that: said lithium source is any one in lithium carbonate, lithium hydroxide or the lithium oxalate.
4. according to claim 2 or 3 described a kind of anode material for lithium-ion batteries, it is characterized in that: the consumption of said 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) is calculated.
5. a kind of anode material for lithium-ion batteries according to claim 1; It is characterized in that: also comprise the doped source compound; In the oxide/hydroxide that said doped source compound is aluminium, chromium or nickel any one, said doped source compound amount accounts for 0～3.0% of system total weight.
6. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 1 comprises the steps:
(1), with manganese source, lithium source and flux ball milling 2～5 hours in ball mill, to ball milling material average grain diameter be 2～12 μ m;
(2), gained ball milling material is put in the saggar, sintering in roller kilns, under air atmosphere with the programming rate heating of 1～20 ℃/min; To 600～780 ℃ of insulation 6～12h; Continue to be warming up to 800～1000 ℃ of insulation 6～12h,, obtain the caking material with the stove cooling;
(3), material to be sintered cooling back pulverizes in pulverizer, being crushed to median diameter is 5～20 μ m, at 600～800 ℃ of insulation 6～12h down, obtains individual particle class spherical lithium manganate target product behind this agglutinating matter of mixing.
7. the preparation method of a kind of anode material for lithium-ion batteries according to claim 6 is characterized in that: the consumption of said 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) is calculated.
8. according to the preparation method of claim 6 or 7 described a kind of anode material for lithium-ion batteries; It is characterized in that: said step also can add the doped source compound in (1); In the oxide/hydroxide that said doped source compound is aluminium, chromium or nickel any one, said doped source compound amount accounts for 0～3.0% of system total weight.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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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. |