CN102394297B - Spherical compound lithium-rich multielement cathode material with core shell structure and preparation method thereof - Google Patents
Spherical compound lithium-rich multielement cathode material with core shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a spherical compound lithium-rich multielement cathode material with a core shell structure. The cathode material has a general formula of Li1+m[(NixCoyMn1-x-y)1-n(Ni0.25Mn0.75)n]1-mO2. The spherical compound lithium-rich multielement cathode material breaks through traditional idea of cladding or doping to improve material performance, and acquires better integrated performance through material structure design by realizing nuclear casing functional composition and complementation. The material combines advantages of nuclear and casing, has high energy density and good rate capability and excellent cyclical stability, and is simply prepared, at low cost and easy for industrialized production; therefore, the material has promising development prospect.
Description
Technical field
The present invention relates to a kind of spherical compound lithium-rich multielement cathode material with core shell structure and preparation method thereof, belong to anode material for lithium-ion batteries and electrochemical field.
Background technology
The at present continuous deterioration of and climatic environment in short supply along with global petroleum resources, human social development is faced with stern challenge.The new-energy automobile of development clean energy-saving is subject to the great attention of countries in the world.The development of new-energy automobile, crucial in its electrical source of power.The advantages such as lithium ion battery has that energy density is large, self discharge is little, memory-less effect, operating voltage range are wide, long service life, non-environmental-pollution are the main electrical source of power of current new-energy automobile.And the crucial electrode material of lithium ion battery is the final decision sexual factor of battery performance, wherein positive electrode is to the having the greatest impact of battery performance, and its cost accounts for 40% left and right of whole battery cost.Therefore, exploitation high-performance, cheap positive electrode have great importance to the development of promotion new-energy automobile and relevant new industry.
Now the anode material for lithium-ion batteries of the marketization mainly contains cobalt acid lithium, lithium manganate having spinel structure, nickle cobalt lithium manganate, LiFePO4 etc.Wherein cobalt acid lithium because of the rare cost of cobalt resource higher, and the shortcoming such as environmental pollution, its development space is hindered, the market share declines, and is progressively substituted; Lithium manganate having spinel structure specific discharge capacity is lower, high temperature cyclic performance shortcoming; Nickle cobalt lithium manganate tertiary cathode material compacted density is on the low side, and its high rate performance and security performance also have much room for improvement; LiFePO4 energy density is not high, and the more serious consistency problem of product existence, hinders it and further develops.Compare with front several positive electrodes, rich lithium polynary positive pole material, because it has height ratio capacity (> 200mAh/g), good cycle performance, the wider scope that discharges and recharges, the with low cost and new advantages such as charge discharge mechanism, is considered to the first-selected positive electrode of lithium ion battery of new generation.XLi in current bibliographical information
2mnO
3(1-x) Li[Ni
0.5mn
0.5] O
2material, because ion and the electron conductivity of Co are large, can obviously improve the high rate performance of material, but Co under high voltage easily and electrolyte generation side reaction, affected the cycle performance of this material.Traditional method of modifying, as coated in surface and doping, can only unilaterally improve high rate performance or the cycle performance of rich lithium polynary positive pole material, but also impact by a relatively large margin the specific discharge capacity of material.Therefore, design and develop new structure, the positive electrode that has height ratio capacity, good high rate performance, excellent cycling stability and applicable extensive industrialization concurrently is most important to the development of lithium ion battery and relevant industries.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of lithium ion battery spherical compound lithium-rich multielement cathode material with core shell structure.
Technical scheme of the present invention is, a kind of preparation method of spherical compound lithium-rich multielement cathode material with core shell structure, and the rich lithium polynary positive pole material of the compound lithium ion battery of described spherical nucleocapsid general formula is expressed as: Li
1+m[(Ni
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n]
1-mo
2, be with LiNi
xco
ymn
1-x-yo
2for core, Li
2mnO
3for the composite construction of shell, 0<x<1 in formula, 0<y<1,0<n<1,0.02≤m≤0.5; Preparation method comprises the following steps:
(1) nickel salt, cobalt salt, manganese salt are mixed with to the mixing salt solution A that total concentration of metal ions is 0.5-3.5mol/L, wherein the mol ratio of Ni:Co:Mn is x:y:1-x-y, 0<x<1 wherein, 0<y<1; Nickel salt, manganese salt are mixed with to the mixing salt solution B that total concentration of metal ions is 0.5-3.5mol/L, and wherein the mol ratio of Ni:Mn is 1:3;
(2) ammoniacal liquor that the aqueous slkali that compound concentration is 0.5-10mol/L respectively and concentration are 0.1-10mol/L;
(3) adopt coprecipitation, first mixing salt solution A, aqueous slkali, ammoniacal liquor are joined in reactor by constant flow pump stream, the mixing speed of controlling in reactor is 50-1500rpm, and reaction temperature is 35-65 ℃, pH value is between 7.0-12.0, makes it crystalline deposit and generates spherical inner core [Ni
xco
ymn
1-x-y] (OH)
2or [Ni
xco
ymn
1-x-y] CO
3;
(4) by constant flow pump, mixing salt solution B, aqueous slkali, ammoniacal liquor stream are joined in reactor, the mixing speed of controlling in reactor is 50-1500rpm, reaction temperature is 35-65 ℃, and pH value is between 7.0-12.0, makes it to grow up on spherical inner core surface the [Ni of one deck densification
0.25mn
0.75] (OH)
2or [Ni
0.25mn
0.75] CO
3shell, obtains the precursor [(Ni of nucleocapsid structure
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n] (OH)
2or [(Ni
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n] CO
3;
(5) precursor filtered, wash, dry, evenly mix with the ratio that Li source compound is 1+m: 1-m in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number, wherein 0.02≤m≤0.5; Under air atmosphere, in 400-600 ℃ of pre-burning 4-10h, then be warmed up to 750-1000 ℃, insulation 6-20h, naturally cools to room temperature, obtains the compound rich lithium polynary positive pole material of spherical nucleocapsid.
Described nickel salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate; Cobalt salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate; Manganese salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate.
Described coprecipitation is hydroxide coprecipitation step or carbonate coprecipitation method.
Described alkali is a kind of or its mixture in NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium acid carbonate, ammonium hydrogencarbonate.
Described lithium source is a kind of or its mixture in lithium carbonate, lithium hydroxide, lithium nitrate.
The present invention has following technique effect, break through traditional material modification and take theory coated and doping, adopt coprecipitation to prepare a kind of spherical compound lithium-rich multielement cathode material with core shell structure, it is compound and complementary that this material is realized the function of core, shell, there is high-energy-density, long circulation life, good high rate performance, with low cost and advantages of environment protection, can meet the demand of the association areas such as electrical source of power for new-energy automobile, this preparation technology is simple, is applicable to extensive industrialization.
Accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum of the compound rich lithium polynary positive pole material of nucleocapsid structure of the present invention and comparative example.
Fig. 2 is the compound rich lithium polynary positive pole material scanning electron microscope sem figure of nucleocapsid structure of the present invention.
The internal structure scanning electron microscope sem figure of the compound rich lithium polynary positive pole material of Fig. 3 nucleocapsid structure of the present invention.
Fig. 4 is the first charge-discharge curve of the compound rich lithium polynary positive pole material of nucleocapsid structure of the present invention and comparative example.
Fig. 5 is the compound rich lithium polynary positive pole material of nucleocapsid structure of the present invention and the specific discharge capacity of comparative example under different multiplying.
Fig. 6 is the cycle performance curve of the compound rich lithium polynary positive pole material of nucleocapsid structure of the present invention and comparative example.
Embodiment
Embodiment 1
(1) by nickelous sulfate, manganese sulfate, cobaltous sulfate is in Ni: Mn: Co (mol ratio)=within 1: 1: 1, ratio is mixed, and is dissolved in deionized water, and being mixed with total concentration of metal ions is the mixing salt solution A of 2.0mol/L; By nickelous sulfate, manganese sulfate is in Ni: Mn (mol ratio)=within 1: 3, ratio is mixed, and is dissolved in deionized water, and being mixed with total concentration of metal ions is the mixing salt solution B of 2.0mol/L; The Na that compound concentration is 2.0mol/l respectively
2cO
3aqueous slkali and concentration are the ammoniacal liquor of 0.8mol/L.
(2) by mixing salt solution A, the Na of preparation in step (1)
2cO
3aqueous slkali, ammoniacal liquor join in reactor by constant flow pump stream, and control mixing speed is 1000rpm, and reaction temperature is 55 ℃, and pH value is 8.0, and the reaction time is 12h, by carbonate coprecipitation, are reacted and are obtained spherical inner core [Ni
1/3mn
1/3co
1/3] CO
3.
(3) again by constant flow pump mixing salt solution B, Na
2cO
3aqueous slkali, ammoniacal liquor stream join in reactor, and control mixing speed is 1000rpm, and reaction temperature is 55 ℃, and pH value is 8.0, makes it at spherical inner core [Ni
1/3mn
1/3co
1/3] CO
3surface grows up to the [Ni of one deck densification
0.25mn
0.75] CO
3shell, the control reaction time is 4h, obtains the precursor [(Ni of nucleocapsid structure
1/3mn
1/3co
1/3)
0.6(Ni
0.25mn
0.75)
0.4] CO
3.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.52: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 8h under air atmosphere, then be warmed up to 850 ℃ and be incubated 12h, obtain the compound rich lithium polynary positive pole material Li of nucleocapsid structure
1.2[(Ni
1/3mn
1/3co
1/3)
0.6(Ni
0.25mn
0.75)
0.2]
0.4o
2.
By X diffraction ray analysis, as shown in Figure 1, product is stratiform α-NaFeO
2structure, space group is R-3m, and each diffraction maximum is sharp-pointed, and degree of crystallinity is higher, between 20 °-25 °, occurs obvious superlattice diffraction maximum; By scanning electron microscope sem figure, as shown in Figures 2 and 3, can find out, resulting product size is the spheric granules of 9 about μ m, kernel size approximately 8 μ m wherein, shell approximately 1 μ m; Adopt atomic absorption spectrography (AAS) (AAS) to analyze product, show that Ni, Mn, the actual mol ratio of Co are 0.298: 0.501: 0.201, product can be expressed as Li
1.2[(Ni
1/3mn
1/3co
1/3)
0.6(Ni
0.25mn
0.75)
0.4]
0.2o
2.
Electro-chemical test shows, the compound rich lithium polynary positive pole material of this nucleocapsid structure has excellent chemical property.In 0.1C, 2.0-4.8V voltage range, first discharge specific capacity is 269mAh/g, sees Fig. 4-a; Under 0.2C, 2.0-4.6V condition, after 50 circulations, capability retention is 99.2%, sees Fig. 5-a; Under 0.5C, 1C, 2C multiplying power, its reversible capacity is respectively 218mAh/g, 185mAh/g, 172mAh/g, sees Fig. 6-a.
Embodiment 2
(1)-(3) step is with embodiment 1.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.37: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 8h under air atmosphere, then be warmed up to 850 ℃ and be incubated 12h, obtain the compound rich lithium polynary positive pole material Li of nucleocapsid structure
1.15[(Ni
1/3mn
1/3co
1/3)
0.6(Ni
0.25mn
0.75)
0.4]
0.85o
2.
Electro-chemical test shows, in 0.1C, 2.0-4.8V voltage range, first discharge specific capacity is 258mAh/g; Under 0.2C, 2.0-4.6V condition, after 100 circulations, capability retention is 96.7%; Under 0.5C, 1C, 2C multiplying power, its reversible capacity is respectively 215mAh/g, 180mAh/g, 168m Ah/g, shows good chemical property.
Embodiment 3
(1) by nickelous sulfate, manganese sulfate, cobaltous sulfate is in Ni: Mn: Co (mol ratio)=within 4: 4: 2, ratio is mixed, and is dissolved in deionized water, and being mixed with total concentration of metal ions is the mixing salt solution A of 2.0mol/L; By nickelous sulfate, manganese sulfate is in Ni: Mn (mol ratio)=within 1: 3, ratio is mixed, and is dissolved in deionized water, and being mixed with total concentration of metal ions is the mixing salt solution B of 2.0mol/L; The ammoniacal liquor that the NaOH aqueous slkali that compound concentration is 4.0mol/l respectively and concentration are 4.0mol/L.
(2) mixing salt solution A, NaOH aqueous slkali, the ammoniacal liquor of preparation in step (1) are joined in the reactor that is full of nitrogen protection by constant flow pump stream; control mixing speed is 1000rpm; reaction temperature is 55 ℃; pH value is 11.0; reaction time is 24h, by carbonate coprecipitation, is reacted and is obtained spherical inner core [Ni
0.4mn
0.4co
0.2] (OH)
2.
(3) by constant flow pump, mixing salt solution B, NaOH aqueous slkali, ammoniacal liquor stream are joined in the reactor that is full of nitrogen protection, control mixing speed is 1000rpm again, and reaction temperature is 55 ℃, and pH value is 11.0, makes it at spherical inner core [Ni
0.4mn
0.4co
0.2] (OH)
2surface grows up to the [Ni of one deck densification
0.25mn
0.75] (OH)
2shell, controls reaction time 2h, obtains the precursor [(Ni of nucleocapsid structure
0.4mn
0.4co
0.2)
0.8(Ni
0.25mn
0.75)
0.2] (OH)
2.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.52: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 6h under air atmosphere, then be warmed up to 800 ℃ and be incubated 12h, obtain the compound rich lithium polynary positive pole material Li of nucleocapsid structure
1.2[(Ni
0.4mn
0.4co
0.2)
0.8(Ni
0.25mn
0.75)
0.2]
0.2o
2.
Electro-chemical test shows, in 0.1C, 2.0-4.8V voltage range, first discharge specific capacity is 256mAh/g; Under 0.2C, 2.0-4.6V condition, after 100 circulations, capability retention is 97.1%; Under 0.5C, 1C, 2C multiplying power, its reversible capacity is respectively 214mAh/g, 185mAh/g, 174mAh/g, shows good chemical property.
Embodiment 4
(1)-(3) step is with embodiment 3.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.37: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 6h under air atmosphere, then be warmed up to 800 ℃ and be incubated 12h, obtain the compound rich lithium polynary positive pole material Li of nucleocapsid nucleocapsid structure
1.15[(Ni
0.4mn
0.4co
0.2)
0.8(Ni
0.25mn
0.75)
0.2]
0.75o
2.
Electro-chemical test shows, in 0.1C, 2.0-4.8V voltage range, first discharge specific capacity is 258mAh/g, under 0.2C, 2.0-4.6V condition, after 100 circulations, capability retention is 96.8%, under 0.5C, 1C, 2C multiplying power, its reversible capacity is respectively 210mAh/g, 182mAh/g, 157mAh/g, shows good chemical property.
(1)-(3) step is with embodiment 3.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.52: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 6h under air atmosphere, then be warmed up to 850 ℃ of insulation 12h, obtain nucleocapsid functional form richness lithium polynary positive pole material Li
1.2[(Ni
0.4mn
0.4co
0.2)
0.6(Ni
0.25mn
0.75)
0.4]
0.8o
2.
Embodiment 6
(1)-(3) step is with embodiment 3.
(4) precursor obtaining in step (3) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.52: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 6h under air atmosphere, then be warmed up to 900 ℃ of insulation 12h, obtain nucleocapsid functional form richness lithium polynary positive pole material Li
1.2[(Ni
0.4mn
0.4co
0.2)
0.7(Ni
0.25mn
0.75)
0.3]
0.8o
2.
Comparative example
Adopt carbonate coprecipitation legal system for the rich lithium polynary positive pole material of general spherical shape Li
1.2[Ni
0.3mn
0.5co
0.2]
0.8o
2.
(1) by nickelous sulfate, manganese sulfate, cobaltous sulfate is in Ni: Mn: Co (mol ratio)=within 3: 5: 2, ratio is mixed, and is dissolved in deionized water, is mixed with the mixing salt solution that total concentration of metal ions is 2.0mol/L; The Na that compound concentration is 2.0mol/L respectively
2cO
3aqueous slkali and concentration are the ammoniacal liquor of 0.4mol/L.
(2) by mixing salt solution, the Na of preparation in step (1)
2cO
3aqueous slkali, ammoniacal liquor join in reactor by constant flow pump stream, and control mixing speed is 1000rpm, and reaction temperature is 55 ℃, and pH value is 8.0, and the reaction time is 24h, by coprecipitation reaction, obtains spherical precursor [Ni
0.3mn
0.5co
0.2] CO
3.
(3) precursor obtaining in step (2) filtered, wash, be dried, with Li
2cO
3after the ratio that is 1.52: 1 in the ratio of the molal quantity of lithium and Ni, Mn, Co total mole number is evenly mixed, 500 ℃ of pre-burning 8h under air atmosphere, then be warmed up to 850 ℃ of insulation 12h, obtain general spherical shape richness lithium polynary positive pole material Li
1.2[Ni
0.3mn
0.5co
0.2]
0.8o
2.
Claims (5)
1. a preparation method for spherical compound lithium-rich multielement cathode material with core shell structure, the rich lithium polynary positive pole material of the compound lithium ion battery of described spherical nucleocapsid general formula is expressed as: Li
1+m[(Ni
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n]
1-mo
2, with Li
1+m[Ni
xco
ymn
1-x-y]
1-mo
2for core, Li
1+m[Ni
0.25mn
0.75]
1-mo
2for the composite construction of shell, 0<x<1 in formula, 0<y<1,0<n<1,0.02≤m≤0.5; Preparation method comprises the following steps:
(1) nickel salt, cobalt salt, manganese salt are mixed with to the mixing salt solution A that total concentration of metal ions is 0.5-3.5mol/L, wherein the mol ratio of Ni:Co:Mn is x:y:1-x-y, 0<x<1 wherein, 0<y<1; Nickel salt, manganese salt are mixed with to the mixing salt solution B that total concentration of metal ions is 0.5-3.5mol/L, and wherein the mol ratio of Ni:Mn is 1:3;
(2) ammoniacal liquor that the aqueous slkali that compound concentration is 0.5-10mol/L respectively and concentration are 0.1-10mol/L;
(3) adopt coprecipitation, first mixing salt solution A, aqueous slkali, ammoniacal liquor are joined in reactor by constant flow pump stream, the mixing speed of controlling in reactor is 50-1500rpm, and reaction temperature is 35-65 ℃, pH value is between 7.0-12.0, makes it crystalline deposit and generates spherical inner core [Ni
xco
ymn
1-x-y] (OH)
2or [Ni
xco
ymn
1-x-y] CO
3;
(4) by constant flow pump, mixing salt solution B, aqueous slkali, ammoniacal liquor stream are joined in reactor, the mixing speed of controlling in reactor is 50-1500rpm, reaction temperature is 35-65 ℃, and pH value is between 7.0-12.0, makes it to grow up on spherical inner core surface the [Ni of one deck densification
0.25mn
0.75] (OH)
2or [Ni
0.25mn
0.75] CO
3shell, obtains the precursor [(Ni of nucleocapsid structure
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n] (OH)
2or [(Ni
xco
ymn
1-x-y)
1-n(Ni
0.25mn
0.75)
n] CO
3;
(5) precursor filtered, wash, dry, evenly mix with the ratio that Li source compound is 1+m:1-m in the molal quantity of lithium and Ni, Mn, the ratio of Co total mole number, wherein 0.02≤m≤0.5; Under air atmosphere, in 400-600 ℃ of pre-burning 4-10h, then be warmed up to 750-1000 ℃, insulation 6-20h, naturally cools to room temperature, obtains the compound rich lithium polynary positive pole material of spherical nucleocapsid.
2. in the preparation method of spherical compound lithium-rich multielement cathode material with core shell structure according to claim 1, it is characterized in that: described nickel salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate; Cobalt salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate; Manganese salt is a kind of or its salt-mixture in sulfate, nitrate, chlorate, acetate.
3. in the preparation method of spherical compound lithium-rich multielement cathode material with core shell structure according to claim 1, it is characterized in that: described coprecipitation is hydroxide coprecipitation step or carbonate coprecipitation method.
4. in the preparation method of spherical compound lithium-rich multielement cathode material with core shell structure according to claim 1, it is characterized in that: described aqueous slkali is a kind of or its mixture in NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium acid carbonate, ammonium bicarbonate solution.
5. in the preparation method of spherical compound lithium-rich multielement cathode material with core shell structure according to claim 1, it is characterized in that: described lithium source is a kind of or its mixture in lithium carbonate, lithium hydroxide, lithium nitrate.
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| CN111018006A (en) * | 2019-12-18 | 2020-04-17 | 多氟多新能源科技有限公司 | Preparation method of core-shell structure high-nickel ternary cathode material |
| CN113428906A (en) * | 2020-03-23 | 2021-09-24 | 浙江林奈新能源有限公司 | Composition, positive electrode material and lithium ion battery |
| CN111916710A (en) * | 2020-08-17 | 2020-11-10 | 中国科学院宁波材料技术与工程研究所 | Composite lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN113328088B (en) * | 2021-05-17 | 2022-06-07 | 湘潭大学 | Controllable method for realizing surface modification of electrode material |
| CN113991079A (en) * | 2021-10-20 | 2022-01-28 | 陈琴雅 | Composite cathode material and preparation method thereof |
| CN114361440A (en) * | 2022-01-07 | 2022-04-15 | 巴斯夫杉杉电池材料有限公司 | High-voltage ternary cathode material with core-shell structure and preparation method thereof |
| CN114772556B (en) * | 2022-06-20 | 2022-11-04 | 天津蓝天太阳科技有限公司 | Porous structure precursor, hollow structure oxide and application in anode material |
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