CN103928664A - Lithium-enriched manganese-based anode material with fast ion conductor coating layer and surface heterostructure and preparation method of lithium-enriched manganese-based anode material - Google Patents
Lithium-enriched manganese-based anode material with fast ion conductor coating layer and surface heterostructure and preparation method of lithium-enriched manganese-based anode material Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a lithium-enriched manganese-based anode material with a fast ion conductor coating layer and a surface heterostructure and a preparation method of the lithium-enriched manganese-based anode material. The surface of the lithium-enriched manganese-based anode material is coated with a coating layer consisting of Li3PO4 and Li4P2O7; a spinel phase nano-crystal is inlaid in the surface of the lithium-enriched manganese-based anode material; the spinel phase nano-crystal and a lithium-enriched layered material form a heterostructure; the lithium-enriched manganese-based anode material has a structural formula of Li1+aMnbMcO2, wherein M is one or more of Ni, Co, Al, Cr, Fe and Mg, 0<=a<=1, 0<=b<=1, and 0<=c<=1. The method comprises the following steps: (1) fully mixing the lithium-enriched manganese-based anode material with a proper amount of phosphate; and (2) sintering the sample which is uniformly mixed in a certain atmosphere, thus obtaining the lithium-enriched manganese-based anode material with the fast ion conductor coating layer and the surface heterostructure. The first coulombic efficiency of the lithium-enriched anode material is improved, the cycling stability and rate performance of the lithium-enriched anode material are improved, and the requirements of a power battery can be met.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries and technical field of electrochemistry, relate to a kind of lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure and preparation method thereof.
Background technology
Lithium ion battery with respect to traditional secondary cell such as lead-acid battery, Ni-MH battery have that energy density is high, output voltage is high, self discharge is low, memory-less effect and advantages of environment protection and be widely used and develop.The performance of power and energy storage lithium ion battery critical material is the final decision sexual factor of battery performance, and the research of positive electrode is the focus that scientific worker pays close attention to always.LiCoO
2, LiMnO
4, LiFePO
4, LiNi
xco
ymn
1-x-yo
2studied widely Deng positive electrode.But there is the defects such as specific energy density is low, cost is high, poor stability in the lithium-ion battery system of these positive electrode assemblings, is difficult to meet the requirement of electric motor car to energy-storage battery.
Lithium-rich manganese-based anode material is greater than the advantages such as 250mAh/g, operating voltage be high, with low cost because its theoretical specific capacity exceedes 350mAh/g, actual specific capacity, is the study hotspot of anode material for lithium-ion batteries always.The shortcoming severe inhibition such as but coulomb efficiency first of lithium-rich manganese-based anode material is low, high rate performance is poor, voltage in cyclic process reduces gradually the large-scale application of lithium-rich manganese-based anode material.
In order to develop the lithium-rich manganese-based anode material of high rate performance excellence, meet the requirement of electric motor car to battery high rate performance, researcher has developed multiple technologies means lithium-rich manganese-based anode material has been carried out to modification raising.Various inert substances are as metal fluoride (AlF
3), metal phosphate (AlPO
4, Li-Ni-PO
4) and metal oxide (Al
2o
3, ZnO, RuO
2deng) etc. be used to coated lithium-rich manganese-based anode material.As the Thackera of Argonne National Laboratory etc. adopts Li-Ni-PO
4coated 0.5Li
2mnO
30.5LiNi
0.44co
0.75mn
0.31o
2efficiency first can be brought up to 87% from 81%, reduce irreversible capacity loss first, under 1C current density, specific discharge capacity exceedes 200mAh/g simultaneously; The Yang Yongs of Xiamen University etc. adopt AlF
3coated Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2, under 2C current density, specific discharge capacity reaches 197mAh/g, and not coated sample only has 177.9mAh/g.Professor Cho has reported Li[Li
0.15mn
0.6ni
0.25] O
2nano-material shows good charge-discharge performance, its first discharge capacity reach 311mAh/g, can keep 280mAh/g through 80 circulations.Professor Sun Shigang of Xiamen University utilizes the synthetic nano-sheet Li[Li with (010) direction preferred orientation of the method for crystal growth
0.17ni
0.25mn
0.58] O
2positive electrode.Can show good cycle performance and high rate performance, under 0.2C discharge scenario, through 100 circulations, its discharge capacity maintains 230mAh/g, and under 6C discharge scenario, through 50 circulations, its discharge capacity maintains 200mAh/g.But harsh preparation technology makes it be difficult to carry out suitability for industrialized production.
Therefore, need badly at present and find a kind of method of modifying of simple lithium-rich manganese-based anode material, make lithium-rich manganese-based anode material there is higher coulomb efficiency first, cyclical stability and high rate performance preferably, thus can meet the requirement of electrokinetic cell.
Summary of the invention
The object of the present invention is to provide a kind of lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure and preparation method thereof.With lithium-rich manganese-based anode material and phosphate mixed sintering, improve coulomb efficiency first of lithium-rich anode material, and improved its cyclical stability and high rate performance, can meet the requirement of electrokinetic cell.Its modified technique is applicable to all lithium-rich manganese-based anode materials, simple, low cost of manufacture, and favorable reproducibility, is convenient to large-scale industrial production.
The object of the invention is to be achieved through the following technical solutions:
A lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure, the surface of described lithium-rich manganese-based anode material is coated with by Li
3pO
4and Li
4p
2o
7the coating layer of composition and be inlaid with Spinel nanocrystal, Spinel nanocrystal and rich lithium stratified material formation heterostructure, wherein the structural formula of lithium-rich manganese-based anode material is Li
1+amn
bm
co
2, M is one or more in Ni, Co, Al, Cr, Fe, Mg, 0≤a≤1,0≤b≤1,0≤c≤1.
There is a preparation method for the lithium-rich manganese-based anode material of fast-ionic conductor coating layer and surface heterogeneous medium structure, at least comprise following two steps:
(1) lithium-rich manganese-based anode material is fully mixed with appropriate phosphate, wherein: lithium-rich manganese-based anode material is Li
1+amn
bm
co
2, wherein M is one or more in Ni, Co, Al, Cr, Fe, Mg, 0≤a≤1,0≤b≤1,0≤c≤1; Phosphate is (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4one or more mixture; Phosphatic addition is the 0.1-20% of lithium-rich manganese-based anode material molal quantity; Hybrid mode is the one of ball milling, grinding, magnetic agitation.
(2), by the sample mixing sintering under certain atmosphere, obtain having the lithium-rich manganese-based anode material of fast-ionic conductor coating layer and surface heterogeneous medium structure; Wherein: mixed sintering temperature is 400-800 DEG C, the rate of heat addition of mixed sintering is 1-10 DEG C/min, the mixed sintering time is 3-8h, and mixed sintering atmosphere is oxygen, argon gas, airborne one, and the gas flow rate in mixed sintering process is 100-500ml/min; Coating layer is by Li
3pO
4and Li
4p
2o
7composition, the Spinel nanocrystal of surface inserting and rich lithium stratified material form heterostructure, thereby make this lithium-rich manganese-based anode material have higher lithium ion transmission coefficient.
Advantage of the present invention is: with lithium-rich manganese-based anode material and phosphate mixed sintering, improved coulomb efficiency first of lithium-rich manganese-based anode material, and improved its cyclical stability and high rate performance, can meet the requirement of electrokinetic cell.Its modified technique is applicable to all lithium-rich manganese-based anode materials, simple, low cost of manufacture, and favorable reproducibility, is convenient to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the XRD figure of lithium-rich manganese-based anode material (embodiment 1) after the front lithium-rich manganese-based anode material (comparative example) of surface phosphoric acid salt modification and the modification of surface phosphoric acid salt;
Fig. 2 is the SEM figure of lithium-rich manganese-based anode material (comparative example) before the modification of surface phosphoric acid salt;
Fig. 3 is the SEM figure of lithium-rich manganese-based anode material (embodiment 2) after the modification of surface phosphoric acid salt;
Fig. 4 is the first charge-discharge curve of lithium-rich manganese-based anode material (embodiment 3 and embodiment 4) after the front lithium-rich manganese-based anode material (comparative example) of surface phosphoric acid salt modification and the modification of surface phosphoric acid salt;
Fig. 5 is the high rate performance curve of lithium-rich manganese-based anode material (embodiment 2) after the front lithium-rich manganese-based anode material (comparative example) of surface phosphoric acid salt modification and the modification of surface phosphoric acid salt;
Fig. 6 is the cyclical stability of lithium-rich manganese-based anode material (embodiment 4) after the front lithium-rich manganese-based anode material (comparative example) of surface phosphoric acid salt modification and the modification of surface phosphoric acid salt.
Embodiment
Further illustrate the present invention below by embodiment and comparative example, these embodiment, just for the present invention is described, the invention is not restricted to following examples.Every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
1, by 5g lithium-rich manganese-based anode material Li
1.2ni
0.13co
0.13mn
0.54o
2and 0.7468gNH
4h
2pO
4fully mix by magnetic agitation;
2, be that 200ml/min, heat temperature raising speed are sintering 5h under 1 DEG C/min, 400 DEG C of conditions of sintering temperature by the material mixing in step 1 at air velocity, finally obtain NH
4h
2pO
4the lithium-rich manganese-based anode material of surface modification.
X-ray diffraction (XRD) analysis shows that product is lithium-rich manganese-based anode material, and material degree of crystallinity is higher, does not have dephasign to generate, and after phosphate modification, has occurred Li
3pO
4phase, Li
4p
2o
7phase and Spinel (seeing Fig. 1), these are present in the surface of lithium-rich manganese-based anode material particle mutually, and Li
3pO
4phase, Li
4p
2o
7phase and Spinel all have higher lithium ion transmission coefficient, so by lithium-rich manganese-based anode material and phosphate mixed sintering, obtain a kind of lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure, this coating layer is by Li
3pO
4and Li
4p
2o
7composition, the Spinel nanocrystal of surface inserting and rich lithium stratified material form heterostructure, thereby make this lithium-rich manganese-based anode material have higher lithium ion transmission coefficient.
Embodiment 2:
1, by 5g lithium-rich manganese-based anode material Li
1.2ni
0.13co
0.13mn
0.54o
2and 0.1867gNH
4h
2pO
4fully mix by magnetic agitation;
2, be that 200ml/min, heat temperature raising speed are sintering 5h under 1 DEG C/min, 400 DEG C of conditions of sintering temperature by the material mixing in step 1 at air velocity, finally obtain NH
4h
2pO
4the lithium-rich manganese-based anode material of surface modification.
Testing prepared lithium-rich manganese-based anode material is spherical morphology, particle integrity, not significantly broken or reunion, granular size is about 15-20um (seeing Fig. 2), and the lithium-rich manganese-based anode material of modification has better kept the spherical morphology (seeing Fig. 3) of lithium-rich manganese-based anode material.
The first coulomb efficiency of the lithium-rich manganese-based anode material of surface phosphoric acid salt modification under 30mA/g current density is 87.0% (seeing Fig. 4), now for lithium-rich manganese-based anode material, irreversible capacity drops to 37.5mAh/g from 68.4mAh/g, coulomb efficiency is brought up to 87.0% (seeing Fig. 4) from 78.7% first, the irreversible capacity first that has reduced lithium-rich manganese-based anode material by the modification of surface phosphoric acid salt is described, has improved coulomb efficiency first.
Under 30mA/g-1000mA/g current density, the specific discharge capacity of the lithium-rich manganese-based anode material of surface phosphoric acid salt modification, apparently higher than original material, illustrates that surperficial phosphate modification has also improved the high rate performance of lithium-rich manganese-based anode material (seeing Fig. 5).
Embodiment 3:
1, by 5g lithium-rich manganese-based anode material Li
1.2ni
0.13co
0.13mn
0.52mg
0.02o
2with 0.2800g NH
4h
2pO
4fully mix by magnetic agitation;
2, by the material mixing in step 1 being that 300ml/min, heat temperature raising speed are sintering 5h under 5 DEG C/min, 500 DEG C of conditions of sintering temperature at air velocity, finally obtain NH
4h
2pO
4the lithium-rich manganese-based anode material of surface modification.
Embodiment 4:
1, by 5g lithium-rich manganese-based anode material Li
1.2ni
0.13co
0.13mn
0.54o
2and 0.3734gNH
4h
2pO
4fully mix by magnetic agitation;
2, be that 200ml/min, heat temperature raising speed are sintering 5h under 1 DEG C/min, 400 DEG C of conditions of sintering temperature by the material mixing in step 1 at air velocity, finally obtain NH
4h
2pO
4the lithium-rich manganese-based anode material of surface modification.
The first coulomb efficiency of the lithium-rich manganese-based anode material of surface phosphoric acid salt modification under 30mA/g current density is 98.2% (seeing Fig. 4), now for lithium-rich anode material, irreversible capacity drops to 5.0mAh/g from 68.4mAh/g, coulomb efficiency is brought up to 98.2% (seeing Fig. 4) from 78.7% first, the irreversible capacity first that has reduced lithium-rich manganese-based anode material by the modification of surface phosphoric acid salt is described, has improved coulomb efficiency first.
Under 150mA/g current density, discharge capacity is 218.3mAh/g first, after 100 circulations, discharge capacity is 200.0mAh/g, conservation rate is 91.6% (seeing Fig. 6), the cyclical stability of the lithium-rich manganese-based anode material of surface phosphoric acid salt modification is obviously better than original lithium-rich manganese-based anode material, and the cyclical stability that has obviously improved lithium-rich manganese-based anode material by the modification of surface phosphoric acid salt is described.
Embodiment 5:
1, by 5g lithium-rich manganese-based anode material Li
1.2ni
01.3co
0.13mn
0.52cr
0.02o
2with 0.2800g NH
4h
2pO
4fully mix by magnetic agitation;
2, by the material mixing in step 1 being that 300ml/min, heat temperature raising speed are sintering 5h under 5 DEG C/min, 500 DEG C of conditions of sintering temperature at air velocity, finally obtain NH
4h
2pO
4the lithium-rich manganese-based anode material of surface modification.
Comparative example: undressed lithium-rich manganese-based anode material Li
1.2ni
0.13co
0.13mn
0.54o
2.
Claims (8)
1. there is a lithium-rich manganese-based anode material for fast-ionic conductor coating layer and surface heterogeneous medium structure, it is characterized in that the surface of described lithium-rich manganese-based anode material is coated with by Li
3pO
4and Li
4p
2o
7the coating layer of composition, is inlaid with Spinel nanocrystal, and wherein the structural formula of lithium-rich manganese-based anode material is Li
1+
amn
bm
co
2, M is one or more in Ni, Co, Al, Cr, Fe, Mg, 0≤a≤1,0≤b≤1,0≤c≤1.
2. the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 1, the structural formula that it is characterized in that described lithium-rich manganese-based anode material is Li
1+
amn
bm
co
2, M is one or more in Ni, Co, Al, Cr, Fe, Mg, 0≤a≤1,0≤b≤1,0≤c≤1.
3. a preparation method for the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure described in the arbitrary claim of claim 1-2, is characterized in that described method step is as follows:
(1) lithium-rich manganese-based anode material is fully mixed with appropriate phosphate, control the 0.1-20% that phosphatic addition is lithium-rich manganese-based anode material molal quantity;
(2) sample mixing is carried out to mixed sintering under certain atmosphere, obtain having the lithium-rich manganese-based anode material of fast-ionic conductor coating layer and surface heterogeneous medium structure; Wherein: mixed sintering temperature is 400-800 DEG C, the mixed sintering time is 3-8h.
4. the preparation method of the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 3, is characterized in that described phosphate is (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4one or more mixture.
5. the preparation method of the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 3, is characterized in that described lithium-rich manganese-based anode material and phosphatic hybrid mode are the one of ball milling, grinding, magnetic agitation.
6. the preparation method of the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 3, is characterized in that described mixed sintering atmosphere is oxygen, argon gas, airborne one.
7. the preparation method of the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 3, is characterized in that the gas flow rate in described mixed sintering process is 100-500ml/min.
8. the preparation method of the lithium-rich manganese-based anode material with fast-ionic conductor coating layer and surface heterogeneous medium structure according to claim 3, the rate of heat addition that it is characterized in that described mixed sintering is 1-10 DEG C/min.
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| CN105428637A (en) * | 2014-09-18 | 2016-03-23 | 宁德时代新能源科技有限公司 | Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material |
| CN105428637B (en) * | 2014-09-18 | 2019-03-29 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and preparation method of anode material thereof |
| JP2016186918A (en) * | 2015-03-27 | 2016-10-27 | トヨタ自動車株式会社 | Method of manufacturing nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| CN105261740A (en) * | 2015-11-24 | 2016-01-20 | 宁德新能源科技有限公司 | Lithium battery cathode material, preparation method thereof and lithium battery including same |
| CN105261740B (en) * | 2015-11-24 | 2019-01-22 | 宁德新能源科技有限公司 | A kind of anode material of lithium battery, preparation method and the lithium ion battery containing the material |
| CN106450194B (en) * | 2016-10-13 | 2019-07-19 | 华南师范大学 | A kind of manganese base shape richness lithium material and its preparation method with uniform lithium phosphate clad |
| CN106450194A (en) * | 2016-10-13 | 2017-02-22 | 华南师范大学 | Manganese-based lamellar lithium-rich material provided with uniform lithium phosphate coating layer and preparation method thereof |
| CN106684369A (en) * | 2017-02-16 | 2017-05-17 | 长沙理工大学 | Sodium ion battery anode material embedded and coated with sodium fast ion conductor and synthetic method thereof |
| CN106684369B (en) * | 2017-02-16 | 2019-10-15 | 长沙理工大学 | Sodium ion battery anode material embedded and coated with sodium fast ion conductor and synthetic method thereof |
| CN107528059A (en) * | 2017-09-01 | 2017-12-29 | 中国科学院物理研究所 | Positive electrode active materials of Phosphate coating spinel structure and its preparation method and application |
| CN107528059B (en) * | 2017-09-01 | 2020-08-04 | 中国科学院物理研究所 | Phosphate-coated spinel-structured positive electrode active material and preparation method and application thereof |
| CN108767229A (en) * | 2018-05-30 | 2018-11-06 | 天津巴莫科技股份有限公司 | Stepped combined rich oxidate for lithium solid-solution material of one kind and preparation method thereof |
| CN108767229B (en) * | 2018-05-30 | 2021-03-23 | 天津巴莫科技股份有限公司 | Step-by-step composite lithium-rich oxide solid solution material and preparation method thereof |
| CN112310354A (en) * | 2019-07-29 | 2021-02-02 | 北京卫蓝新能源科技有限公司 | Lithium battery composite positive electrode material and preparation method thereof |
| CN110611091A (en) * | 2019-09-27 | 2019-12-24 | 北京理工大学 | Method for improving electrochemical performance of lithium-rich manganese-based positive electrode material |
| CN112952063A (en) * | 2021-03-10 | 2021-06-11 | 昆山宝创新能源科技有限公司 | Lithium-rich manganese-based composite cathode material and preparation method and application thereof |
| CN113328080A (en) * | 2021-06-10 | 2021-08-31 | 广东工业大学 | Double-coated lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN113328080B (en) * | 2021-06-10 | 2022-03-22 | 广东工业大学 | Double-coated lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN113823786A (en) * | 2021-09-30 | 2021-12-21 | 中国矿业大学(北京) | Modified lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN114639821A (en) * | 2022-03-20 | 2022-06-17 | 北京工业大学 | Surface modification method of monocrystal-like gradient lithium-rich manganese-based layered oxide |
| CN115692656A (en) * | 2022-11-01 | 2023-02-03 | 国联汽车动力电池研究院有限责任公司 | Lithium ion conductor coated high Mn complex phase positive electrode material and preparation method thereof |
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