CN103500824A - Surface-anionic-modified lithium-manganese-based anode material and preparation method thereof - Google Patents
Surface-anionic-modified lithium-manganese-based anode material and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a surface-anionic-modified lithium-manganese-based anode material and a preparation method of the surface-anionic-modified lithium-manganese-based anode material. The method comprises the following steps: step1, fully and uniformly mixing a lithium-manganese-based anode material with ammonium salt; step2, heating a sample uniformly mixed in the step 1 for 1-8 hours at 300-700 DEG C, and obtaining the surface-anionic-modified anode active material. The invention also provides the surface-anionic-modified lithium-manganese-based anode material prepared by the preparation method. The surface-anionic-modified lithium-manganese-based anode material and the preparation method of the surface-anionic-modified lithium-manganese-based anode material can significantly improve the primary coulombic efficiency, the cycling stability and the rate performance of the active material, and a preparation process is very simple and is easy for large scale production.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, particularly, relate to anion-modified lithium-rich manganese-based anode material in a kind of surface and preparation method thereof.
Background technology
Lithium ion battery has become the most excellent, the most widely used battery of commercialization secondary chemical sources of electric energy performance, but all have higher requirement to the specific energy of lithium ion battery as Aerospace Satellite, aircraft and civilian use electric car etc. in various application scenarios, such as NASA and SAFT etc. is defined as the specific energy target of recent lithium ion battery 250 ~ 300Wh/kg, in Japanese NEDO power battery of electric vehicle development plan, also mean will reach 250Wh/kg to the energy density of the year two thousand twenty energy type lithium ion battery.And traditional cobalt acid lithium/graphite body series lithium ion battery can't meet this specific energy index, therefore certainly will need the height ratio capacity electrode material of development of new.In the Olivine-type Cathode Material in Li-ion Batteries of researching and developing at present, lithium-rich manganese-based anode material up to more than 250mAh/g, is considered to the energy-density lithium ion battery positive electrode of new generation of follow-up most possible acquisition application due to specific discharge capacity.
Lithium-rich manganese-based anode material can be regarded as by stratiform Li
2mnO
3with stratiform multicomponent material LiMO
2the solid-solution material that (M=Mn, Co, Ni) forms, although this material has the LiCoO of approaching
2(140mAh/g) height ratio capacity of twice, but still have first that coulombic efficiency is lower, cycle performance and a problem such as high rate performance is poor.Simultaneously, the operating voltage that lithium-rich manganese-based anode material is high (2-4.8V) is easy to make electrolyte to decompose, and at positive pole-electrolyte interface, forms thicker SEI film, increases the internal resistance of cell, affects circulating battery stability.
Therefore need to carry out surface modification to lithium-rich manganese-based anode material, on the one hand can the structural stability of reinforcing material when high voltage discharges and recharges, reduce irreversible capacity loss, improve specific discharge capacity and the cycle performance of active material; On the other hand, can also prolection material itself, suppress under high voltage and the reacting of electrolyte, improve positive pole-electrolyte interface performance, improve battery performance.
The report of existing multiple positive electrode surface modifying method in prior art, be all mainly to adopt oxide, phosphate or material with carbon element to coat processing to active material, thereby improve cycle performance and the high rate performance of positive electrode itself.But surface coated method all can be introduced coating layer, especially oxide and Phosphate coating layer are all the poor materials of conductivity (comprising electronic conductance and ionic conductance), and conductivity missionary society increases surface charge and transmits resistance, hinders Li
+diffusion, increase battery polarization, reduces high rate performance.Process a small amount of report is also arranged for the surface fluorination of positive electrode, use F
2, ClF
3and NF
3deng positive electrode being carried out to charge/discharge capacity, coulombic efficiency and the cycle performance that suitable processing can improve material.But the problem of bringing is, degree of fluorination is large, and complex process requires comparatively strictly to experimental condition as temperature, pressure etc., and surface easily forms the larger fluorinated film of impedance, and the fluorinated source adopted is larger to the human injury.
Summary of the invention
The purpose of this invention is to provide a kind of lithium-rich manganese-based anode material anion-modified for the surface of lithium ion battery and preparation method thereof; lay particular emphasis on the optimizing surface method of modifying; on the basis that does not increase surface coating layer; introduce anion lithium-rich manganese-based anode material is carried out to surface modification; adopt ammonium salt as negative ion source, can realize the weak replacement of positive electrode surface anion, modified effect is even; and technique is very simple, is easy to large-scale production.
In order to achieve the above object, the invention provides the preparation method of the anion-modified lithium-rich manganese-based anode material in a kind of surface, wherein, the method comprises: step 1 fully mixes lithium-rich manganese-based anode material with ammonium salt; Step 2, by the sample mixed in step 1, at 300 ℃ ~ 700 ℃ heat treated 1 ~ 8h, make the anion-modified positive electrode active materials in surface.
The preparation method of the lithium-rich manganese-based anode material that above-mentioned surface is anion-modified, wherein, the described ammonium salt of step 1 is one or more the mixture in ammonium fluoride, ammonium acid fluoride, ammonium sulfide.
The preparation method of the lithium-rich manganese-based anode material that above-mentioned surface is anion-modified, wherein, the described ammonium salt molal quantity of step 1 is 0.1% ~ 20% of positive active material molal quantity.
The preparation method of the lithium-rich manganese-based anode material that above-mentioned surface is anion-modified, wherein, the described lithium-rich manganese-based anode material of step 1 is xLi
2mnO
3(1-x) [LiNi
yco
zmn
(1-y-z)o
2]; 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤y+z≤1.
The preparation method of the lithium-rich manganese-based anode material that above-mentioned surface is anion-modified, wherein, the described heat treated of step 2, the rate of heat addition is 1 ℃/min ~ 5 ℃/min, temperature retention time is 1 ~ 8h, preferably 1 ~ 5h.
The anion-modified lithium-rich manganese-based anode material in surface that the present invention also provides a kind of above-mentioned preparation method to make.
Lithium-rich manganese-based anode material that surface provided by the invention is anion-modified and preparation method thereof has the following advantages:
It is negative ion source that the present invention adopts ammonium salt, lithium-rich manganese-based anode material is carried out to surface anion-modified, and modified effect is gentle, evenly, and technique is simple, is easy to suitability for industrialized production.After modification, coulombic efficiency first, cyclical stability and the high rate performance of material significantly improves.
The accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of embodiment 1, wherein, and before A is modification, after B is modification.
Fig. 2 is the first charge-discharge curve chart (discharging and recharging voltage range 2.0 ~ 4.8V with 0.1C) of embodiment 1, wherein, and before A is modification, after B is modification.
Fig. 3 is the cycle performance curve (discharging and recharging voltage range 2.0 ~ 4.8V with 0.1C) of embodiment 1, wherein, and before A is modification, after B is modification.
Fig. 4 is the cycle performance curve (discharging and recharging voltage range 2.0 ~ 4.8V with 0.1C) of embodiment 2, wherein, and before A is modification, after B is modification.
Fig. 5 is the high rate performance curve (charging/discharging voltage scope 2.0 ~ 4.8V) of embodiment 2, wherein, and before A is modification, after B is modification.
Fig. 6 is the cycle performance curve (discharging and recharging voltage range 2.0 ~ 4.8V with 0.1C) of embodiment 3, wherein, and before A is modification, after B is modification.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described.
The preparation method of the lithium-rich manganese-based anode material that surface provided by the invention is anion-modified comprises: step 1 fully mixes lithium-rich manganese-based anode material with ammonium salt; Step 2, by the sample mixed in step 1, at 300 ℃ ~ 700 ℃ heat treated 1 ~ 8h, make the anion-modified positive electrode active materials in surface.
The ammonium salt of step 1 is one or more the mixture in ammonium fluoride, ammonium acid fluoride, ammonium sulfide.
The ammonium salt molal quantity of step 1 is 0.1% ~ 20% of positive active material molal quantity.
The lithium-rich manganese-based anode material of step 1 is xLi
2mnO
3(1-x) [LiNi
yco
zmn
(1-y-z)o
2]; 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤y+z≤1 wherein.
The heat treated temperature of step 2 is 300 ℃ ~ 700 ℃, and the rate of heat addition is 1 ℃/min ~ 5 ℃/min, and temperature retention time is 1 ~ 8h, preferably 1 ~ 5h.
The anion-modified lithium-rich manganese-based anode material in surface that the present invention also provides a kind of above-mentioned preparation method to make.
Embodiment 1
Take respectively 50g positive electrode Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2and 0.3136gNH
4f, ball milling mixing 5h, rotating speed 200r/min; The sample that ball milling is mixed is at 500 ℃ of lower heat treatment 4h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2as shown in Figure 1, before and after visible modification, crystal structure does not change X-ray diffraction (XRD) figure before and after surface fluorination and modification.
Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2first charge-discharge curve before and after surface fluorination and modification and cycle performance curve are as shown in Figures 2 and 3, before modification, raw-material first discharge specific capacity is 244.1mAh/g as seen from the figure, coulombic efficiency is 86.5% first, 0.1C, 2 ~ 4.8V is while discharging and recharging, after circulating 50 weeks, capability retention is 90.1%; Lithium-rich manganese-based anode material first discharge specific capacity after surface fluorination is brought up to 260.5mAh/g, and coulombic efficiency 92.0% first, and when 0.1C, 2 ~ 4.8V discharge and recharge, after circulating 50 weeks, capability retention reaches 97.1%.
Embodiment 2
Take respectively 50g positive electrode Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2and 0.1254gNH
4f, ball milling mixing 5h, rotating speed 100r/min; The sample that ball milling is mixed is at 400 ℃ of lower heat treatment 2h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2cycle performance curve before and after surface fluorination and modification as shown in Figure 4, can see that the front raw-material first discharge specific capacity of modification is 244.1mAh/g, and when 0.1C, 2 ~ 4.8V discharge and recharge, after circulating 50 weeks, capability retention is 90.1%; Lithium-rich manganese-based anode material first discharge specific capacity after surface fluorination is 265.3mAh/g, and when 0.1C, 2 ~ 4.8V discharge and recharge, after circulating 50 weeks, capability retention reaches 93.2%.
Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2as shown in Figure 5, the positive electrode after surface fluorination is when 0.1C, 0.2C, 0.3C, 0.5C, 1C and 2C as seen from the figure for high rate performance curve before and after surface fluorination and modification, and specific discharge capacity all significantly increases than raw-material capacity, and high rate performance is better.
Embodiment 3
Take respectively 50g positive electrode Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2and 0.2305g (NH
4)
2s, ball milling mixing 10h, rotating speed 100r/min; The sample that ball milling is mixed is at 500 ℃ of lower heat treatment 4h, and heating rate is 1 ℃/min, obtains the lithium-rich manganese-based anode material of surface sulfide.
Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2cycle performance curve before and after the surface sulfide modification as shown in Figure 6, can see that the front raw-material first discharge specific capacity of modification is 244.1mAh/g, and when 0.1C, 2 ~ 4.8V discharge and recharge, after circulating 50 weeks, capability retention is 90.1%; Lithium-rich manganese-based anode material first discharge specific capacity after surface sulfide is 243.2mAh/g, and when 0.1C, 2 ~ 4.8V discharge and recharge, after circulating 50 weeks, capability retention reaches 98.3%.
Embodiment 4
Take respectively 50g positive electrode Li[Li
0.13mn
0.47ni
0.2co
0.2] O
2and 0.1254gNH
4f, ball milling mixing 5h, rotating speed 100r/min; The sample that ball milling is mixed is at 600 ℃ of lower heat treatment 2h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
Embodiment 5
Take respectively 50g positive electrode Li[Li
0.13mn
0.47ni
0.2co
0.2] O
2and 0.5762g (NH
4)
2s, ball milling mixing 10h, rotating speed 100r/min; The sample that ball milling is mixed is at 600 ℃ of lower heat treatment 5h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface sulfide.
Embodiment 6
Take respectively 50g positive electrode Li[Li
0.13mn
0.47ni
0.2co
0.2] O
2and 0.6270gNH
4f, ball milling mixing 5h, rotating speed 200r/min; The sample that ball milling is mixed is at 500 ℃ of lower heat treatment 4h, and heating rate is 1 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
Embodiment 7
Take respectively 50g positive electrode Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2and 0.3304gNH
4h
2f, ball milling mixing 5h, rotating speed 200r/min; The sample that ball milling is mixed is at 500 ℃ of lower heat treatment 4h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
Embodiment 8
Take respectively 50g positive electrode Li[Li
0.2mn
0.54ni
0.13co
0.13] O
2and 0.1652gNH
4h
2f, ball milling mixing 5h, rotating speed 200r/min; The sample that ball milling is mixed is at 400 ℃ of lower heat treatment 2h, and heating rate is 2 ℃/min, obtains the lithium-rich manganese-based anode material of surface fluorination.
The prepared lithium-rich manganese-based anode material of lithium-rich manganese-based anode material preparation method that surface provided by the invention is anion-modified, the anion-modified rear crystal structure in surface does not all change, after modification, coulombic efficiency first, specific discharge capacity and the cyclical stability of material all is improved, and high rate performance significantly improves.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (6)
1. the preparation method of the anion-modified lithium-rich manganese-based anode material in a surface, is characterized in that, the method comprises:
Step 1, fully mix lithium-rich manganese-based anode material with ammonium salt;
Step 2, by the sample mixed in step 1, at 300 ℃ ~ 700 ℃ heat treated 1 ~ 8h, make the anion-modified positive electrode active materials in surface.
2. the preparation method of the anion-modified lithium-rich manganese-based anode material in surface as claimed in claim 1, is characterized in that, the described ammonium salt of step 1 is one or more the mixture in ammonium fluoride, ammonium acid fluoride, ammonium sulfide.
3. the preparation method of the anion-modified lithium-rich manganese-based anode material in surface as claimed in claim 2, is characterized in that, the described ammonium salt molal quantity of step 1 is 0.1% ~ 20% of positive active material molal quantity.
4. the preparation method of the anion-modified lithium-rich manganese-based anode material in surface as claimed in claim 3, is characterized in that, the described lithium-rich manganese-based anode material of step 1 is xLi
2mnO
3(1-x) [LiNi
yco
zmn
(1-y-z)o
2]; 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤y+z≤1 wherein.
5. the preparation method of the anion-modified lithium-rich manganese-based anode material in surface as claimed in claim 1, is characterized in that, the described heat treated of step 2, and the rate of heat addition is 1 ℃/min ~ 5 ℃/min, temperature retention time is 1 ~ 8h.
6. the anion-modified lithium-rich manganese-based anode material in surface made according to the described preparation method of any one in claim 1 ~ 5.
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| CN105355843A (en) * | 2015-11-27 | 2016-02-24 | 上海空间电源研究所 | Method for modifying high-specific-energy lithium ion cell cathode material |
| CN105470509A (en) * | 2015-12-22 | 2016-04-06 | 合肥融捷能源材料有限公司 | Novel NCA material and preparation method thereof |
| CN106410135A (en) * | 2016-09-22 | 2017-02-15 | 北京科技大学 | Surface treatment modified lithium-rich manganese-based layered cathode material and preparation method |
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| CN105140510A (en) * | 2015-09-08 | 2015-12-09 | 上海空间电源研究所 | Lithium ion battery NCA cathode material with surface fluorination processing and preparation method thereof |
| CN105355843A (en) * | 2015-11-27 | 2016-02-24 | 上海空间电源研究所 | Method for modifying high-specific-energy lithium ion cell cathode material |
| CN105470509A (en) * | 2015-12-22 | 2016-04-06 | 合肥融捷能源材料有限公司 | Novel NCA material and preparation method thereof |
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| CN109994712A (en) * | 2017-12-29 | 2019-07-09 | 湖北九邦新能源科技有限公司 | A kind of nickelic tertiary cathode material and its method of modifying, lithium ion battery that surface is modified |
| CN109994712B (en) * | 2017-12-29 | 2022-04-08 | 湖北九邦新能源科技有限公司 | Surface-modified high-nickel ternary cathode material, modification method thereof and lithium ion battery |
| CN108963212A (en) * | 2018-06-28 | 2018-12-07 | 内蒙古华夏新材料科技有限公司 | A kind of anode material for lithium ion battery surface fluorination and modification process |
| CN111697208A (en) * | 2019-03-15 | 2020-09-22 | 南开大学 | Modified lithium ion battery anode material and preparation method thereof |
| CN111697208B (en) * | 2019-03-15 | 2024-03-19 | 南开大学 | Modified lithium ion battery anode material and preparation method thereof |
| CN111224090A (en) * | 2020-03-12 | 2020-06-02 | 河南电池研究院有限公司 | Composite lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN111224090B (en) * | 2020-03-12 | 2022-08-05 | 河南电池研究院有限公司 | Composite lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN111816864A (en) * | 2020-06-02 | 2020-10-23 | 广东工业大学 | Lithium-rich layered oxide composite cathode material and preparation method and application thereof |
| CN111816864B (en) * | 2020-06-02 | 2022-06-03 | 广东工业大学 | Lithium-rich layered oxide composite cathode material and preparation method and application thereof |
| CN114068911A (en) * | 2020-07-30 | 2022-02-18 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel cathode material and preparation method thereof |
| CN114068911B (en) * | 2020-07-30 | 2023-06-20 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel positive electrode material and preparation method thereof |
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