CN103474628A - Carbon-coated ternary positive electrode material and preparation method thereof - Google Patents
Carbon-coated ternary positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon-coated ternary positive electrode material and a preparation method thereof. The preparation method comprises the following steps: S1, preparing a ternary positive electrode material precursor by taking nickel salt, cobalt salt and manganese salt as raw materials; S2, preparing a conductive carbon dispersion system, wherein conductive carbon is dispersed in water containing an organic carbon source; S3, adding the ternary positive electrode material precursor and a lithium compound into the conductive carbon dispersion system, and mixing uniformly to obtain a mixture; S4, drying the mixture under a vacuum condition; S5, carrying out high temperature treatment on the dried mixture under a closed condition or in an inert gas protection atmosphere so as to obtain the carbon-coated ternary positive electrode material. The carbon-coated ternary positive electrode material is uniform in coating, simple to operate, low in cost and high in efficiency; the conductive carbon and the ternary positive electrode material are simultaneously coated with network-shaped amorphous carbon which serves as a conductive medium or a channel of the conductive carbon and the ternary positive electrode material, thereby greatly improving the rate performance of the ternary positive electrode material.
Description
Technical field
The present invention relates to the lithium ion battery material technical field, relate in particular to preparation method and this carbon that carbon that a kind of lithium ion battery uses coats tertiary cathode material and coat tertiary cathode material.
Background technology
Lithium ion battery has a series of advantages such as specific energy is high, operating voltage is high, fail safe is good, memory-less effect, not only the extensive use electrical source of power of the portable type electronic products such as this computer, digital camera, mobile phone, video camera of taking notes, also will become one of main power source of electric bicycle, battery-operated motor cycle and electric automobile simultaneously.This provides broad space for the development of lithium ion battery on the one hand, constantly widening and continuous upgrading and the replacement of corresponding product along with the battery applications field on the other hand, will propose more and more higher requirement to lithium ion battery, and the most direct way of raising battery combination property is to improve the battery material performance.
Positive electrode, as one of battery core parts, plays key effect to the battery combination property, therefore carries out the positive electrode study on the modification significant.Material modification mainly contains two approach: one is doping vario-property, another surface coating modification, and wherein the surface coating is a kind of modified method relatively more commonly used in industrialization.
In the electrokinetic cell field, the research of positive electrode cycle characteristics and high rate performance be two important research directions of material modification, as patent ZL200610147247.1: the nanometer LiCoO that a kind of carbon coats
2material and its preparation method and application, disclose and passed through at LiCoO
2surface is covered carbon and is improved the material electrical conductivity, optimizes the rate charge-discharge performance of material.And the conductivity of current tertiary cathode material is poorer than the sour lithium of cobalt, still remain to be improved.And, have now in battery manufacturing process and often corpuscular conductive carbon and corpuscular positive electrode are mechanically mixed, the defect that this mixing exists conductive carbon can not effectively contact with positive electrode, thus cause electronics not move smoothly, the high rate performance of restriction material.
In the existing modification to tertiary cathode material, also comprise the method that adopts organic carbon to coat tertiary cathode material, the coating of this kind of method just can be coated after need to adopting catalyst to organic carbon emulsification, and method of operation is complicated and have relatively high expectations.
Summary of the invention
The technical problem to be solved in the present invention is, provide a kind of simple to operate, cost is low and improved the high rate performance of material and preparation method and this carbon that the carbon of cycle performance coats tertiary cathode material coat tertiary cathode material.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of carbon to coat the preparation method of tertiary cathode material, comprise the following steps:
S1, to take nickel salt, cobalt salt and manganese salt be raw material, prepares the tertiary cathode material presoma;
S2, preparation conductive carbon dispersion: conductive carbon is scattered in the water that contains organic carbon source;
S3, described tertiary cathode material presoma and lithium compound are joined in described conductive carbon dispersion, mix, obtain mixture;
S4, described mixture is dried under vacuum condition;
S5, by the described mixture of drying in confined conditions or in the atmosphere of inert gas shielding, in 500-1100 ℃ of lower high-temperature process; Described tertiary cathode material presoma forms tertiary cathode material, described conductive carbon is distributed in described tertiary cathode material surface, described organic carbon source forms has network-like amorphous carbon, and described conductive carbon and tertiary cathode material are coated, and obtains carbon and coats tertiary cathode material.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S1, the chemical formula of the described tertiary cathode material presoma made is Ni
xco
ymn
1-x-y(OH)
2; In step S5, the chemical formula of the described tertiary cathode material of formation is LiNi
xco
ymn
1-x-yo
2; Wherein, 0<x<1,0<y<1, and x+y<1.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S1, the sulfate that described nickel salt is nickel, nitrate or hydrochloride, the sulfate that described cobalt salt is cobalt, nitrate or hydrochloride, sulfate, nitrate or hydrochloride that described manganese salt is manganese.
Coat in the preparation method of tertiary cathode material at carbon of the present invention, in step S1, adopt half liquid half to consolidate method described raw material is made to the tertiary cathode material presoma; Described half liquid half method admittedly is first described nickel salt, cobalt salt and manganese salt to be mixed with to mixed solution, adopts liquid-phase precipitation method to obtain the pulp-like mixture of described nickel salt, cobalt salt and manganese salt, then adopts the low-temperature solid phase reaction method to obtain described tertiary cathode material presoma; The mixed solution concentration of described nickel salt, cobalt salt and manganese salt is 0.2-5mol/L.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S2, the mass volume ratio between described conductive carbon and the described water that contains organic carbon source is 1:10-100;
In the described water that contains organic carbon source, the weight percentage of organic carbon source is 10-80%.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S2, described conductive carbon is one or more in graphite, carbon nano-tube, Graphene, acetylene carbon black and superconduction carbon black, and described organic carbon source is one or more in sucrose, glucose, polyacrylic acid, starch, polyethylene glycol and resorcinol;
In step S3, described lithium compound is one or more in lithium carbonate, lithium hydroxide and lithium chloride.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S3, the mass ratio of the conductive carbon in described tertiary cathode material presoma and conductive carbon dispersion is 99.5:0.5-95:5.
At carbon of the present invention, coat in the preparation method of tertiary cathode material, in step S5, the gas flow of described inert gas is 0.05-0.2L/min; Described inert gas is one or more in nitrogen and argon gas.
The present invention also provides a kind of carbon to coat tertiary cathode material, adopts above-mentioned carbon to coat the tertiary cathode material preparation method and makes.
The present invention also provides a kind of carbon to coat tertiary cathode material, comprise tertiary cathode material, conductive carbon and there is network-like amorphous carbon, described conductive carbon is distributed in described tertiary cathode material surface, and described amorphous carbon coats described conductive carbon and tertiary cathode material.
Implement the present invention and there is following beneficial effect:
1, the present invention is used in conjunction with to prepare carbon coating tertiary cathode material by conductive carbon and organic carbon source, organic carbon source high-temperature process under anoxia condition forms has network-like amorphous carbon, by conductive carbon with together with tertiary cathode material coats simultaneously, amorphous carbon serves as conductive media or the passage of conductive carbon and tertiary cathode material therein, has improved widely the high rate performance of this tertiary cathode material.
2, amorphous carbon has good electric conductivity, its coating on tertiary cathode material, not only increase the electron conduction of tertiary cathode material, and the crystal growth of tertiary cathode material can also suppress high-temperature process the time, be conducive to tertiary cathode material and form evengranular nano-scale particle, shorten the migration path of electronics and ion, thereby improve the high rate performance of tertiary cathode material; Also effectively suppress tertiary cathode material charge and discharge process crystal lattice distortion degree, thereby obviously improved high rate performance and the stable circulation performance of this tertiary cathode material, improved cycle performance of lithium ion battery.
3, amorphous carbon can effectively reduce the contact area of tertiary cathode material and electrolyte, has suppressed the reactivity of tertiary cathode material and electrolyte, has improved the security performance of tertiary cathode material.And the network-like of amorphous carbon can also effectively adsorb electrolyte, is conducive to improve the migration rate of lithium ion, thus the high rate performance of raising tertiary cathode material.
4, preparation method of the present invention has the advantages that coating is even, simple to operate, cost is low and efficiency is high, is suitable for industrialization.In addition, the adding of conductive carbon in the present invention, can reduce the operation that adds conductive carbon and dispersed electro-conductive carbon in follow-up tertiary cathode material application process, improve the battery make efficiency.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the flow chart that carbon of the present invention coats the preparation method of tertiary cathode material;
Fig. 2 is the SEM figure that carbon of the present invention coats tertiary cathode material;
Fig. 3 is the high rate performance curve chart that the carbon that uses the present invention to make coats the lithium ion battery of tertiary cathode material;
Fig. 4 is the cycle performance curve chart that the carbon that uses the present invention to make coats the lithium ion battery of tertiary cathode material.
Embodiment
As shown in Figure 1, carbon of the present invention coats the preparation method of tertiary cathode material, comprises the steps:
S1, to take nickel salt, cobalt salt and manganese salt be raw material, prepares the tertiary cathode material presoma.
In this step S1, the soluble-salts such as the sulfate that nickel salt is nickel, nitrate or hydrochloride, the soluble-salts such as the sulfate that cobalt salt is cobalt, nitrate or hydrochloride, the soluble-salts such as the sulfate that manganese salt is manganese, nitrate or hydrochloride.Adopt half liquid half to consolidate method raw material is made to the tertiary cathode material presoma; This half liquid half method admittedly is first nickel salt, cobalt salt and manganese salt to be mixed with to mixed solution, adopts liquid-phase precipitation method to obtain the pulp-like mixture of nickel salt, cobalt salt and manganese salt, then adopts the low-temperature solid phase reaction method to obtain the tertiary cathode material presoma.The chemical formula of the tertiary cathode material presoma made is Ni
xco
ymn
1-x-y(OH)
2, wherein, 0<x<1,0<y<1, and x+y<1; Can be as 0.2≤x≤0.4,0.3≤y≤0.7 etc.When preparing the tertiary cathode material presoma, the mixed solution concentration of the nickel salt of preparing, cobalt salt and manganese salt is 0.2-5mol/L.
S2, preparation conductive carbon dispersion: conductive carbon is scattered in the aqueous solution that contains organic carbon source.
In this step S2, conductive carbon is dispersed in method in the water that contains organic carbon source can adopt in ultrasonic method, mechanical mixing method and ball-milling method one or more, jitter time is 15-60min(minute), this jitter time is not limited to 15-60min, be uniformly dispersed as long as reach, be less than 15min or all can more than 60min.Mass volume ratio (g/ml) between conductive carbon and the water that contains organic carbon source is 1:10-100.In containing the water of organic carbon source, the weight percentage of organic carbon source is 10-80%.Wherein, conductive carbon is one or more in graphite, carbon nano-tube, Graphene, acetylene carbon black and superconduction carbon black, organic carbon source be in sucrose, glucose, polyacrylic acid, starch, polyethylene glycol and resorcinol one or more.
S3, tertiary cathode material presoma and lithium compound are joined in the conductive carbon dispersion, mix, obtain mixture.
In this step S3, lithium compound is one or more in lithium carbonate, lithium hydroxide and lithium chloride.The mass ratio of the conductive carbon in tertiary cathode material presoma and conductive carbon dispersion is 99.5:0.5-95:5, can adopt according to actual needs the corresponding mass ratio, is preferably 99:1-97:3.
S4, mixture is dried under vacuum condition.
In this step S4, the temperature of oven dry is 50-200 ℃, preferably 60-100 ℃; Time is 0.1-10h(hour), preferred 2-5h.
S5, by the mixture of drying high-temperature process in confined conditions or in the atmosphere of inert gas shielding, obtain carbon and coat tertiary cathode material, described high temperature is 500-1100 ℃.
In this step S5; the mixture of drying can be placed in the high temperature furnace of inert gas shielding and be processed; or do not need inert gas shielding and be placed in airtight high temperature furnace and process and also can; purpose is that the tertiary cathode material presoma is formed to tertiary cathode material, and makes organic carbon source form amorphous carbon through the high temperature dehydration carbonization.During high-temperature process, wherein the oxygen of a little can be arranged in closed environment, the oxygen that guarantees a little does not contribute to the tertiary cathode material presoma to form tertiary cathode material when not affecting organic carbon source dehydration carbonization.Described high temperature is preferably 800-950 ℃; Processing time is 1-15h, is preferably 6-10h.In the atmosphere of inert gas shielding, during high-temperature process, inert gas is one or more in nitrogen and argon gas.The gas flow of inert gas is 0.05-0.2L/min; This gas flow is that inert gas is 1m by area
2the gas flow in cross section.
Therefore, in this step S5, after high-temperature process, the tertiary cathode material presoma forms tertiary cathode material, conductive carbon is distributed in the tertiary cathode material surface, organic carbon source forms has network-like amorphous carbon, and conductive carbon and tertiary cathode material are coated, and obtains carbon and coats tertiary cathode material.Wherein, the chemical formula of the tertiary cathode material of formation is LiNi
xco
ymn
1-x-yo
2, wherein, 0<x<1,0<y<1, and x+y<1; Can be as 0.2≤x≤0.4,0.3≤y≤0.7 etc.Organic carbon source forms amorphous carbon through high-temperature process dehydration carbonization under anoxia condition, on the tertiary cathode material surface, forms uniform thin layer conductive layer, is conducive to increase the electron conduction of tertiary cathode material, thereby improves the high rate performance of this material.And the amorphous carbon of this formation has network-like, by network-like, conductive carbon and tertiary cathode material are coated togather, increased conductive media or the electron transfer passage of tertiary cathode material and conductive carbon, be conducive to improve the high rate performance of tertiary cathode material.When this amorphous carbon can also suppress high-temperature process, the growth of the crystal of tertiary cathode material, be conducive to tertiary cathode material and form evengranular nano-scale particle, shortens the migration path of electronics and ion, thereby improve the high rate performance of tertiary cathode material.This amorphous carbon is coated on the surperficial also efficiency of tertiary cathode material and suppresses the crystal lattice distortion of this material in charge and discharge process, thereby improves the cycle performance of tertiary cathode material; This amorphous carbon can also effectively reduce the contact area of tertiary cathode material and electrolyte, has suppressed the reactivity of this material and electrolyte, thereby has improved the security performance of tertiary cathode material; The network-like of amorphous carbon can also effectively adsorb electrolyte, is conducive to improve the migration rate of lithium ion, thereby improves the high rate performance of tertiary cathode material.
Preparation method of the present invention has the advantages that coating is even, simple to operate, cost is low and efficiency is high, is suitable for industrialization.The present invention adds conductive carbon in the process of synthesis of ternary positive electrode, is conducive to the equally distributed while of conductive carbon, has also reduced the operation that adds conductive carbon and dispersed electro-conductive carbon in the subsequent material application process, improves the battery make efficiency.
As shown in Figure 2, the carbon that above-mentioned preparation method makes coats tertiary cathode material, can comprise tertiary cathode material 1, conductive carbon 2 and have network-like amorphous carbon 3, conductive carbon 2 is distributed in tertiary cathode material 1 surface, and setting carbon 3 coats this tertiary cathode material 1 and conductive carbon 2 get up.This amorphous carbon 3 is formed through high-temperature process dehydration carbonization under anoxia condition by organic carbon source.
Below by specific embodiment, the invention will be further described.
Embodiment 1
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 0.2mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
1/3co
1/3mn
1/3(OH)
2;
S2, employing mechanical mixing method are scattered in 5 gram graphite in the aqueous solution (weight percentage of sucrose is 10%) of 500 gram sucrose, stir 15 minutes, obtain the conductive carbon dispersion;
S3,125 gram tertiary cathode material presomas and 55 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 50 ℃, vacuumize under condition, dry 10 hours;
S5, by the mixture of oven dry high-temperature process 15 hours in the high temperature furnace that 500 ℃, nitrogen flow are 0.2L/min, obtain carbon and coat tertiary cathode material.
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 0.5mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
1/3co
1/3mn
1/3(OH)
2;
S2, employing mechanical mixing method are scattered in 4 gram acetylene carbon blacks in the aqueous solution (weight percentage of glucose is 30%) of 300 gram glucose, and mixing time is 30 minutes;
S3,76 gram tertiary cathode material presomas and 45 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 60 ℃, vacuumize under condition, dry 5 hours;
S5, by the mixture of drying high-temperature process 10 hours in 800 ℃, airtight high temperature furnace, obtain carbon and coat tertiary cathode material.
Embodiment 3
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 1mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
0.4co
0.4mn
0.2(OH)
2;
S2, employing mechanical mixing method are by 3 gram carbon nanotube disperseds in the aqueous solution (weight percentage of sucrose is 50%) of 250 gram sucrose, and mixing time is 40 minutes;
S3,97 gram tertiary cathode material presomas and 45 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 100 ℃, vacuumize under condition, dry 2 hours;
S5, by the mixture of oven dry high-temperature process 10 hours in the high temperature furnace that 800 ℃, nitrogen flow are 0.1L/min, obtain carbon and coat tertiary cathode material.
Embodiment 4
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 3mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
0.3co
0.6mn
0.1(OH)
2;
S2, employing mechanical mixing method are by 5 gram carbon nanotube disperseds in the aqueous solution (weight percentage of sucrose is 70%) of 50 gram sucrose, and mixing time is 45 minutes;
S3,125 gram tertiary cathode material presomas and 55 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 150 ℃, vacuumize under condition, dry 3 hours;
S5, by the mixture of drying high-temperature process 6 hours in 950 ℃, airtight high temperature furnace, obtain carbon and coat tertiary cathode material.
Embodiment 5
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 5mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
0.2co
0.7mn
0.1(OH)
2;
S2, employing mechanical mixing method are by 5 gram carbon nanotube disperseds in the aqueous solution (weight percentage of starch is 80%) of 300 gram starch, and mixing time is 60 minutes;
S3,125 gram tertiary cathode material presomas and 55 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 200 ℃, vacuumize under condition dry 30min;
S5, by the mixture of oven dry high-temperature process 1 hour in the high temperature furnace that 1100 ℃, nitrogen flow are 0.05L/min, obtain carbon and coat tertiary cathode material.
Embodiment 6
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 4mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
0.2co
0.7mn
0.1(OH)
2;
S2, employing mechanical mixing method are scattered in 2 gram acetylene carbon blacks in the aqueous solution (weight percentage of glucose is 60%) of 100 gram glucose, and mixing time is 15 minutes;
S3,198 gram tertiary cathode material presomas and 60 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 80 ℃, vacuumize under condition, dry 4 hours;
S5, by the mixture of drying high-temperature process 8 hours in 900 ℃, airtight high temperature furnace, obtain carbon and coat tertiary cathode material.
Embodiment 7
S1, by the mixed solution of nickelous sulfate, cobaltous sulfate and the manganese sulfate of stoichiometric proportion preparation 3mol/L, adopt the half liquid half presoma Ni of the standby tertiary cathode material of legal system admittedly
0.2co
0.7mn
0.1(OH)
2;
S2, employing mechanical mixing method are scattered in 3 gram acetylene carbon blacks in the aqueous solution (weight percentage of glucose is 80%) of 300 gram glucose, and mixing time is 20 minutes;
S3,597 gram tertiary cathode material presomas and 200 gram lithium carbonates are added in the conductive carbon dispersion, adopt mechanical mixing method that it is mixed, obtain mixture;
S4, by mixture obtained above at 160 ℃, vacuumize under condition, dry 3 hours;
S5, by the mixture of oven dry high-temperature process 2 hours in the high temperature furnace that 1000 ℃, nitrogen flow are 0.2L/min, obtain carbon and coat tertiary cathode material.
In above-described embodiment, the high temperature furnace volume can be 1m
3, the area of section that wherein nitrogen passes through is about 1m
2.Coat tertiary cathode material by the prepared carbon of above-described embodiment 1-7, can be as shown in Figure 2.The carbon made with embodiment 1 coats the lithium ion battery of tertiary cathode material, adopts the high rate performance of new prestige test grading system at the test battery of normal temperature and pressure, and its high rate performance curve chart can be as shown in Figure 3; Wherein, transverse axis is the battery capacity conservation rate, and the longitudinal axis is voltage, and five curves are followed successively by the curve under 3.0C, 2.0C, 1.0C, 0.5C and 0.2C condition from top to bottom.From figure, curve is known, at 0.2C(the top curve) battery capacity conservation rate 100%, at 0.5C battery capacity conservation rate 98%, at 1.0C battery capacity conservation rate 95%, at 2.0C battery capacity conservation rate 92%, in the lower curve of 3.0C() battery capacity conservation rate 88%, thus this carbon of known use coats the lithium ion battery of tertiary cathode material, has high rate capability.
At normal temperatures and pressures, with the electric current of 1C, the lithium ion battery that uses this carbon to coat tertiary cathode material is carried out to charge and discharge cycles, adopt the capacity circulating of new Weir test cabinet test, carry out loop test 1000 times, the curve chart of testing time and capability retention as shown in Figure 4, therefrom known, after 1000 magnetic cycle tests, the capability retention 83% of battery, cycle performance is high.
The high rate performance curve that the lithium ion battery of the carbon coating tertiary cathode material made with embodiment 2 to embodiment 7 is measured and cycle performance curve and embodiment 1 are roughly the same, all have than high rate capability and cycle performance.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various changes, combination and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in claim scope of the present invention.
Claims (10)
1. the preparation method of a carbon coating tertiary cathode material, is characterized in that, comprises the following steps:
S1, to take nickel salt, cobalt salt and manganese salt be raw material, prepares the tertiary cathode material presoma;
S2, preparation conductive carbon dispersion: conductive carbon is scattered in the water that contains organic carbon source;
S3, described tertiary cathode material presoma and lithium compound are joined in described conductive carbon dispersion, mix, obtain mixture;
S4, described mixture is dried under vacuum condition;
S5, by the described mixture of drying in confined conditions or in the atmosphere of inert gas shielding, in 500-1100 ℃ of lower high-temperature process; Described tertiary cathode material presoma forms tertiary cathode material, described conductive carbon is distributed in described tertiary cathode material surface, described organic carbon source forms has network-like amorphous carbon, and described conductive carbon and tertiary cathode material are coated, and obtains carbon and coats tertiary cathode material.
2. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S1, the chemical formula of the described tertiary cathode material presoma made is Ni
xco
ymn
1-x-y(OH)
2; In step S5, the chemical formula of the described tertiary cathode material of formation is LiNi
xco
ymn
1-x-yo
2; Wherein, 0<x<1,0<y<1, and x+y<1.
3. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S1, the sulfate that described nickel salt is nickel, nitrate or hydrochloride, the sulfate that described cobalt salt is cobalt, nitrate or hydrochloride, sulfate, nitrate or hydrochloride that described manganese salt is manganese.
4. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S1, adopts half liquid half to consolidate method described raw material is made to the tertiary cathode material presoma;
Described half liquid half method admittedly is first described nickel salt, cobalt salt and manganese salt to be mixed with to mixed solution, adopts liquid-phase precipitation method to obtain the pulp-like mixture of described nickel salt, cobalt salt and manganese salt, then adopts the low-temperature solid phase reaction method to obtain described tertiary cathode material presoma;
The mixed solution concentration of described nickel salt, cobalt salt and manganese salt is 0.2-5mol/L.
5. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S2, the mass volume ratio between described conductive carbon and the described water that contains organic carbon source is 1:10-100;
In the described water that contains organic carbon source, the weight percentage of organic carbon source is 10-80%.
6. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S2, described conductive carbon is one or more in graphite, carbon nano-tube, Graphene, acetylene carbon black and superconduction carbon black, and described organic carbon source is one or more in sucrose, glucose, polyacrylic acid, starch, polyethylene glycol and resorcinol;
In step S3, described lithium compound is one or more in lithium carbonate, lithium hydroxide and lithium chloride.
7. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S3, the mass ratio of the conductive carbon in described tertiary cathode material presoma and conductive carbon dispersion is 99.5:0.5-95:5.
8. carbon according to claim 1 coats the preparation method of tertiary cathode material, it is characterized in that, in step S5, the gas flow of described inert gas is 0.05-0.2L/min; Described inert gas is one or more in nitrogen and argon gas.
9. a carbon coats tertiary cathode material, it is characterized in that, the preparation method who adopts the described carbon of claim 1-9 any one to coat tertiary cathode material makes.
10. a carbon coats tertiary cathode material, it is characterized in that, comprise tertiary cathode material, conductive carbon and have network-like amorphous carbon, described conductive carbon is distributed in described tertiary cathode material surface, and described amorphous carbon coats described conductive carbon and tertiary cathode material.
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| CN105118986A (en) * | 2015-08-28 | 2015-12-02 | 洛阳理工学院 | Preparation method for nickel-cobalt lithium manganate serving as high-performance lithium ion battery positive electrode material |
| CN105140470A (en) * | 2015-07-10 | 2015-12-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nanotube @ ternary @ silver composite material of lithium-ion battery |
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