CN103996851A - Preparation method of lithium ion battery positive pole active material - Google Patents
Preparation method of lithium ion battery positive pole active material Download PDFInfo
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- CN103996851A CN103996851A CN201410208987.6A CN201410208987A CN103996851A CN 103996851 A CN103996851 A CN 103996851A CN 201410208987 A CN201410208987 A CN 201410208987A CN 103996851 A CN103996851 A CN 103996851A
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- C01B9/00—General methods of preparing halides
- C01B9/08—Fluorides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a preparation method of a lithium ion battery positive pole material, which comprises the following steps: providing metal particles, a fluorine-containing oxygen-free compound and an oxygen-free carbon source; mixing the metal particles, fluorine-containing oxygen-free compound and oxygen-free carbon source to obtain a mixture; and sintering the mixture in an inert atmosphere to obtain a carbon-coated metal fluoride, wherein the fluorine-containing oxygen-free compound is decomposed to release hydrogen fluoride gas in the sintering process.
Description
Technical field
The present invention relates to anode active material of lithium ion battery field, be specifically related to a kind of preparation method of metal fluoride positive electrode active materials.
Background technology
Lithium ion battery extensive use in portable electronic products at present, but need it to there is higher energy density at electric automobile and extensive energy storage field, therefore need seek the anode active material of lithium ion battery of high-energy-density.Anode active material of lithium ion battery cobalt acid lithium or the LiFePO4 of commercialization at present only limit to an electronics redox reaction, therefore its specific capacity is lower.
Metal fluoride can carry out polyelectron redox reaction, therefore have higher specific capacity.Simultaneously metal fluoride has the strong covalent bond (M-F key) between metallic atom and fluorine atom and the higher redox voltage that brings, so, metal fluoride has higher theoretical energy density, is the alternative positive electrode active materials of lithium ion battery with high energy density.But, the M-F key of metal fluoride is a kind of high electronegativity valence link, make metal fluoride there is larger energy gap, make metal fluoride non-conductive, while being applied to anode active material of lithium ion battery, also have the problems such as the coulombic efficiency causing because of volumetric expansion is low, cycle performance is poor.
In order to overcome the existing problem of metal fluoride positive electrode active materials, wherein a kind of solution is to increase the conductivity of metal fluoride at the coated carbon-coating of metal fluoride particle surface, and cushions the change in volume in its charge and discharge process.But the existing method at metal fluoride coated with carbon bed is for directly will at high temperature carrying out sintering after metal fluoride and carbon source mixing, this method not only can make metal fluoride be easy to oxidized and generate impurity, and the carbon-coating that this method forms is amorphous carbon layer, the conductivity of amorphous carbon layer is poor, and the chemical property of therefore adopting the carbon-clad metal fluoride of preparing is in this way still poor.
Summary of the invention
In view of this, necessaryly provide that a kind of preparation method is simple, cost is lower, be applicable to the preparation method that suitability for industrialized production can improve the metal fluoride positive electrode active materials of metal fluoride electric conductivity simultaneously.
A preparation method for anode active material of lithium ion battery, comprising:
Metallic particles, fluorine-containing non-oxygen compound and anaerobic carbon source are provided;
This metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source are mixed to get to a mixture; And
This mixture is carried out in inert atmosphere to sintering, obtain carbon-clad metal fluoride, this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas in described sintering process.
The present invention carries out sintering after metallic particles, fluorine-containing non-oxygen compound and anaerobic carbon source are mixed again, synchronously complete the growth of metal fluoride and being coated of carbon-coating, compared with prior art, preparation method's technique of the present invention simply, easily operation and cost lower, applicable to large-scale industrial production; In addition, preparation method of the present invention can form graphitization carbon-coating at metal fluoride particle surface, this graphitization carbon-coating can provide for metal fluoride space and the more electron transport passage of more volumetric expansion and contraction, therefore, metal fluoride positive electrode active materials prepared by the present invention not only has higher specific capacity and energy density, possesses good electric conductivity, higher coulombic efficiency and more stable cycle performance simultaneously.
Accompanying drawing explanation
Fig. 1 is first embodiment of the invention metal fluoride positive electrode active materials preparation method's flow chart.
Fig. 2 is second embodiment of the invention metal fluoride positive electrode active materials preparation method's flow chart.
Fig. 3 is that third embodiment of the invention is at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride preparation method's flow chart.
Fig. 4 is that fourth embodiment of the invention is at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride preparation method's flow chart.
Fig. 5 is the stereoscan photograph of the coated ferrous fluoride nucleocapsid compound of the embodiment of the present invention 1 carbon.
Fig. 6 is the XRD resolution chart of the coated ferrous fluoride nucleocapsid compound of the embodiment of the present invention 1 carbon.
Fig. 7 is the transmission electron microscope photo of the coated ferrous fluoride nucleocapsid compound of the embodiment of the present invention 1 carbon.
Fig. 8 is the stereoscan photograph of the coated ferrous fluoride nucleocapsid compound of the embodiment of the present invention 2 carbon.
Fig. 9 is the coated ferrous fluoride nucleocapsid compound of the embodiment of the present invention 2 carbon and the cycle performance test comparison figure that does not carry out the coated ferrous fluoride of carbon.
Embodiment
Refer to Fig. 1, first embodiment of the invention provides a kind of preparation method of metal fluoride positive electrode active materials, comprising:
S11, provides metallocene and fluorine-containing non-oxygen compound;
S12, is mixed to get one first mixture by this metallocene and this fluorine-containing non-oxygen compound; And
S13 carries out sintering by this first mixture in inert atmosphere, obtains carbon-clad metal fluoride.
In step S11, this metallocene is the transition metal formed organo-metallic compound that is connected with cyclopentadiene.Typical metallocene is to be formed by connecting by two cyclopentadienyls and divalence oxidation state metal center, and general formula is (C
5h
5)
2m.This metallocene can be decomposed into metal simple-substance and carbon clusters in described sintering process.Described carbon clusters refers to the atomic group that ten to hundreds of carbon atoms form, and this carbon clusters has higher reactivity.Preferably, this metallocene can be one or more in ferrocene, cobaltocene, dicyclopentadienyl nickel and two luxuriant manganese.
This metallocene is solid.The pattern of this metallocene is not limit, and for example this metallocene can be Powdered.The granularity of this metallocene is less, is more conducive to the carrying out of decomposition reaction in follow-up sintering process.Preferably, the granularity of this metallocene is less than or equal to 200 orders.
This fluorine-containing non-oxygen compound can discharge hydrogen fluoride gas in the process of heating or sintering.In addition, this fluorine-containing non-oxygen compound occurs to decompose and discharges the impurity of remaining impurity for easily removing after hydrogen fluoride gas, and for example this impurity can be gas, and except hydrogen fluoride, other described impurity does not participate in generating the reaction of metal fluoride.This fluorine-containing non-oxygen compound can be fluorine-containing one or more without in oxygen organic and fluorine-containing anaerobic inorganic matter.Preferably, this fluorine-containingly can be in Kynoar (PVDF), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), polyvinyl fluoride (PVF) and one or more of trifluoromethylbenzene without oxygen organic.This fluorine-containing anaerobic inorganic matter can be NH
4f and NH
4hF
2in one or more.
This fluorine-containing non-oxygen compound can be solid (for example PVDF), also can be liquid (for example trifluoromethylbenzene).When this fluorine-containing non-oxygen compound is solid, the pattern of this fluorine-containing non-oxygen compound is not limit.Preferably, this fluorine-containing non-oxygen compound can be Powdered.The granularity of this fluorine-containing non-oxygen compound is less, is more conducive to the carrying out of decomposition reaction in follow-up sintering process.Preferably, the granularity of this fluorine-containing non-oxygen compound is less than or equal to 200 orders.
In step S12, as long as the hybrid mode that the fluorine-containing non-oxygen compound of this metallocene and this is mixed can make the fluorine-containing non-oxygen compound of this metallocene and this mix.This metallocene can mix at normal temperatures with this fluorine-containing non-oxygen compound.Preferably, metallocene can mix with this fluorine-containing non-oxygen compound under the environment of anaerobic, with the metal pentafluoride composition granule that prevents from sneaking into oxygen in this first mixture and make to generate in follow-up sintering process, is oxidized.In one embodiment, solid-state metallocene can be immersed in liquid fluorine-containing non-oxygen compound and form a suspension, thereby form the fluorine-containing non-oxygen compound film of one deck on this solid-state metallocene surface, obtain described the first mixture.In one embodiment, also solid-state metallocene can be dissolved in the fluorine-containing non-oxygen compound of described liquid state and form a mixed solution, obtain described the first mixture.In another embodiment, the metallocene of solid powdery and the fluorine-containing non-oxygen compound of solid powdery or liquid can be taked the method for grinding or ball milling to mix.Preferably, this metallocene adopts the method for ball milling to mix with this fluorine-containing non-oxygen compound, adopt the method for ball milling can not only make the fluorine-containing non-oxygen compound of this metallocene and this mix, also can further reduce the granularity of this metallocene or this fluorine-containing non-oxygen compound, more be conducive to the carrying out of decomposition reaction in follow-up sintering process.Preferably, this metallocene and this fluorine-containing non-oxygen compound are solid.
Metallic element in this metallocene has a minimum non-zero valence state m+.The mixed proportion of this metallocene and this fluorine-containing non-oxygen compound is (m-0.1) according to the stoichiometric proportion of fluorine element and metallic element: 1 to (m+0.1): 1 carries out proportioning.Preferably, in this metallocene and this fluorine-containing non-oxygen compound, the stoichiometric proportion of fluorine element and metallic element is (m-0.1): 1 to m:1, the hydrogen fluoride that within the scope of this, described fluorine-containing non-oxygen compound decomposition produces can total overall reaction generate metal fluoride, can not produce unnecessary hydrogen fluoride gas.
In step S13, the temperature of described sintering is for making this metallocene and this fluorine-containing non-oxygen compound that the temperature of decomposing all can occur.Preferably, described sintering temperature is 400 ° of C to 1000 ° of C.More preferably, described sintering temperature is 500 ° of C to 900 ° of C.The most preferably, described sintering temperature is 600 ° of C to 800 ° of C.If described sintering temperature is too low, formed carbon-coating degree of graphitization is lower; If described sintering temperature is too high, described metal fluoride is oxidizable.The time of described sintering is 1 hour to 10 hours.Preferably, described sintering time is 2 hours to 5 hours.If described sintering time is too short, above-mentioned reaction is insufficient, if described sintering time is long, described metal fluoride is oxidizable.This inert atmosphere can further protect the metal fluoride of generation not oxidized.Preferably, this inert atmosphere can be one or more in argon gas, nitrogen and helium.
In described sintering process, there is to decompose generation metal simple-substance and carbon clusters in this metallocene, this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas, this metal simple-substance and the reaction of this hydrogen fluoride gas generate metal pentafluoride composition granule, simultaneously, the surface that this carbon clusters is adsorbed onto this metal pentafluoride composition granule forms carbon coating layer, has finally formed the core-shell structure of carbon-clad metal fluoride.
The carbon-coating of described carbon-clad metal fluoride is even continuous carbon-coating.Due to the existence of this metal simple-substance in described sintering process, can there is graphitization in this carbon clusters, so this carbon-coating is graphitization carbon-coating in the process that forms carbon-coating.Owing to thering is the existence of the carbon clusters of reproducibility in described sintering process, the least significant non-zero valence state m+ that in this carbon-clad metal fluoride, the valence state of metallic element is this metallic element.
The carbon-coating thickness of this carbon-clad metal fluoride is 5nm to 50nm.Preferably, the carbon-coating thickness of this carbon-clad metal fluoride is 10nm to 20nm.The quality of this carbon-coating is 30% to 60% of this carbon-clad metal fluoride quality.Preferably, the quality of this carbon-coating is 30% to 40% of this carbon-clad metal fluoride quality.Carbon-coating in this mass range, when improving the conductivity of this metal fluoride, can guarantee that this metal fluoride has higher capacity.The mass percent that ratio that can be by regulating and controlling carbon and metallic element in described the first mixture accounts for this carbon-clad metal fluoride to the thickness of this carbon-coating and this carbon-coating regulates and controls.
When this fluorine-containing non-oxygen compound is fluorine-containing anaerobic inorganic matter, this carbon-clad metal fluoride is spheric granules.The diameter of the carbon-clad metal fluoride of this spheric granules is 50nm to 1 μ m.This may be because the decomposition temperature of this fluorine-containing anaerobic inorganic matter is lower, decomposition rate is very fast, in described sintering process, can produce fast more hydrogen fluoride gas, therefore this metal fluoride crystal can be grown at each crystal face from the beginning, has finally formed the metal fluoride of spheric granules.
When this fluorine-containing non-oxygen compound is fluorine-containing during without oxygen organic, this carbon-clad metal fluoride is rod-shpaed particle.Therefore in addition, because this is fluorine-containing, without oxygen organic, also can in described sintering process, decomposite carbon clusters, can obtain the carbon-clad metal fluoride of the thicker carbon-coating of thickness in the scope of above-mentioned 5nm to 50nm.The length of the carbon-clad metal fluoride of this rod-shpaed particle is 500nm to 1.2 μ m, and width is 50nm to 1 μ m.This may be because the organic decomposition temperature of this fluorine-containing anaerobic is higher, decomposition rate is slower, the amount that in the process that has just started to grow in metal fluoride crystal, hydrogen fluoride gas produces is less, therefore this metal fluoride crystal is preferentially grown along a crystal face, thereby has formed the metal fluoride of rod-shpaed particle.
First embodiment of the invention is by carrying out sintering after metallocene and the mixing of fluorine-containing non-oxygen compound again, synchronously complete the growth of metal fluoride and being coated of carbon-coating, compared with prior art, preparation method's technique of the present invention simply, easily operation and cost lower, applicable to large-scale industrial production.
Because the boiling point of this metallocene is lower, generally lower than 300 ° of C, this metallocene can distillation form gas in described sintering process, therefore after reacting with hydrogen fluoride gas, can form the less and uniform metal pentafluoride composition granule of granularity, finally form the less and uniform carbon-clad metal fluoride particles of granularity.
Because described sintering carries out in inert atmosphere, and do not contain oxygen element in this fluorine-containing non-oxygen compound, simultaneously described metallocene decomposes the carbon clusters generating and has reproducibility, therefore can there is not oxidation and generate the impurity such as metal oxide in this metal simple-substance and this metal pentafluoride composition granule in described sintering process, thereby can obtain the metal pentafluoride composition granule that purity is higher.
In addition, the carbon-coating of this carbon-clad metal fluoride is even continuous graphitization carbon-coating, compare with amorphous carbon layer, this graphitization carbon-coating can provide space and the more electron transport passage of more volumetric expansion and contraction for metal fluoride, make metal fluoride have better electric conductivity.Therefore, metal fluoride positive electrode active materials prepared by the present invention not only has higher specific capacity and energy density, possesses good electric conductivity, higher coulombic efficiency and more stable cycle performance simultaneously.
Refer to Fig. 2, second embodiment of the invention provides a kind of preparation method who prepares metal fluoride positive electrode active materials, comprising:
S21, provides metallic particles, described fluorine-containing non-oxygen compound and anaerobic carbon source;
S22, is mixed to get one second mixture by this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source; And
S23 carries out sintering by this second mixture in inert atmosphere, obtains carbon-clad metal fluoride.
In step S21, this metallic particles is simple substance, can be a kind of in Ti, V, Mn, Fe, Bi, Co, Ni, Cu, Zn, Sn, Ag, Pb, Ca or Ba particle.This metallic particles can be nano particle.Preferably, the particle diameter of this metallic particles can be between 20nm to 1 μ m.Preferably, in order to obtain, particle diameter is less, the better positive electrode active materials of performance, and the particle diameter of this metallic particles can be between 20nm to 500nm.This metallic particles can adopt the methods such as aqueous solution reducing process, sol-gel process, vapour deposition process, evaporation-coacervation and pyrolysis metallic compound to be prepared.
Metallic element in this metallic particles has a minimum non-zero valence state m+.The mixed proportion of this metallic particles and this fluorine-containing non-oxygen compound is (m-0.1) according to the stoichiometric proportion of fluorine element and metallic element: 1 to (m+0.1): 1 carries out proportioning.Preferably, in this metallocene and this fluorine-containing non-oxygen compound, the stoichiometric proportion of fluorine element and metallic element is (m-0.1): 1 to m:1, the hydrogen fluoride that within the scope of this, this fluorine-containing non-oxygen compound decomposition produces can total overall reaction generate metal fluoride, can not produce unnecessary hydrogen fluoride gas.
Described anaerobic carbon source can be solid, also can be liquid.Preferably, described anaerobic carbon source can decomposite carbon clusters in described sintering process.Preferably, described anaerobic carbon source can be one or more in polyethylene, polypropylene, polystyrene, polyphenyl naphthalene, Kynoar, polytetrafluoroethylene, fluorinated ethylene propylene copolymer and polyvinyl fluoride.Oxygen-free element in described anaerobic carbon source therefore can not make metallic particles oxidation occur and generate metal oxide impurities in described sintering process.
In step S22, as long as the hybrid mode that this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source are mixed can make this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source mix.This metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source can be mixed at normal temperatures.Preferably, this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source can be mixed under the environment of anaerobic, with the metal pentafluoride composition granule that prevents from sneaking into oxygen in described the second mixture and make to generate in follow-up sintering process, are oxidized.Preferably, this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source are solid, the metallic particles of this solid, fluorine-containing non-oxygen compound and anaerobic carbon source can be taked the method for grinding or ball milling to mix.Preferably, this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source adopt the method for ball milling to mix, adopt the method for ball milling can not only make this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source mix, also can further reduce the granularity of this metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source, more be conducive to the carrying out of sintering reaction in follow-up sintering process.
In step S23, the temperature of described sintering is for making this anaerobic carbon source and this fluorine-containing non-oxygen compound that the temperature of decomposing all can occur.Preferably, described sintering temperature is 400 ° of C to 1000 ° of C.More preferably, described sintering temperature is 500 ° of C to 900 ° of C.The most preferably, described sintering temperature is 600 ° of C to 800 ° of C.If described sintering temperature is too low, formed carbon-coating degree of graphitization is lower; If described sintering temperature is too high, described metal fluoride is easily oxidized.The time of described sintering is 1 hour to 10 hours.Preferably, described sintering time is 2 hours to 5 hours.If described sintering time is too short, above-mentioned reaction is insufficient, if described sintering time is long, described metal fluoride is oxidizable.This inert atmosphere can further protect the metal fluoride of generation not oxidized.Preferably, this inert atmosphere can be one or more in argon gas, nitrogen and helium.
In described sintering process, this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas, and generation carbon clusters occurs to decompose this anaerobic carbon source.This metallic particles and the reaction of this hydrogen fluoride gas generate metal pentafluoride composition granule, and meanwhile, the surface that this carbon clusters is adsorbed onto this metal pentafluoride composition granule forms carbon coating layer, has finally formed the core-shell structure of carbon-clad metal fluoride.
The carbon-coating of described carbon-clad metal fluoride is even continuous carbon-coating.Due to the existence of this metallic particles in described sintering process, can there is graphitization in this carbon clusters, so this carbon-coating is graphitization carbon-coating in the process that forms carbon-coating.Owing to thering is the existence of the carbon clusters of reproducibility in described sintering process, the least significant non-zero valence state m+ that the valence state of metallic element described in this metal fluoride positive electrode active materials is this metallic element.
Second embodiment of the invention is carried out sintering after metallic particles, fluorine-containing non-oxygen compound and anaerobic carbon source are mixed again, synchronously complete the growth of metal fluoride and being coated of carbon-coating, compared with prior art, preparation method's technique of the present invention simply, easily operation and cost lower, applicable to large-scale industrial production.
Because described sintering carries out in inert atmosphere, and do not contain oxygen element in this fluorine-containing non-oxygen compound and this anaerobic carbon source, therefore can there is not oxidation and generate the impurity such as metal oxide in this metal simple-substance and this metal pentafluoride composition granule in described sintering process, can obtain the metal pentafluoride composition granule that purity is higher.
In addition, the carbon-coating of this carbon-clad metal fluoride is even continuous graphitization carbon-coating, compare with amorphous carbon layer, this graphitization carbon-coating can provide space and the more electron transport passage of more volumetric expansion and contraction for metal fluoride, make described metal fluoride have better electric conductivity.Therefore, metal fluoride positive electrode active materials prepared by the present invention not only has higher specific capacity and energy density, possesses good electric conductivity, higher coulombic efficiency and more stable cycle performance simultaneously.
Second embodiment of the invention is carried out sintering after also described metallic compound, described fluorochemical and described anaerobic carbon source can being mixed and is prepared carbon-clad metal fluoride, in described sintering process, can there is to decompose the less metallic particles of generation particle diameter in this metallic compound, thereby for the preparation of metal fluoride positive electrode active materials provides metallic particles, and can obtain the metal fluoride positive electrode active materials that particle diameter is less.
In addition, the present invention also can provide a kind of preparation method at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride layer, this metal fluoride layer can avoid this lithium-transition metal oxide positive electrode active materials and the direct of electrolyte to contact, suppress reacting between this lithium-transition metal oxide positive electrode active materials and electrolyte, prevent this lithium-transition metal oxide positive electrode active materials in use capacity reduce fast, can improve cycle performance and the high rate capability of the lithium ion battery that uses this lithium-transition metal oxide positive electrode active materials simultaneously.
Refer to Fig. 3, third embodiment of the invention further provides a kind of preparation method at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride, comprising:
S31, provides described metallic particles, described fluorine-containing non-oxygen compound and lithium-transition metal oxide positive electrode active materials;
S32, is mixed to get one the 3rd mixture by this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials; And
S33 carries out sintering by the 3rd mixture in inert atmosphere, obtains the coated lithium-transition metal oxide positive electrode active materials of metal fluoride.
In step S31, this lithium-transition metal oxide positive electrode active materials for can reversibly insert and deviate from the lithium intercalation compound of lithium ion in charging and discharging lithium battery process.Described lithium-transition metal oxide positive electrode active materials can be one or more in LiMn2O4, layered lithium manganate, lithium nickelate, cobalt acid lithium, LiFePO4, Li, Ni, Mn oxide and the lithium nickel cobalt manganese oxide of the spinel structure of doping or doping not.Particularly, the LiMn2O4 of this spinel structure can be by chemical formula Li
xmn
2-yl
yo
4represent, this lithium nickelate can be by chemical formula Li
xni
1-yl
yo
2represent, the chemical formula of this cobalt acid lithium can be by Li
xco
1-yl
yo
2represent, the chemical formula of this layered lithium manganate can be by Li
xmn
1-yl
yo
2, the chemical formula of this LiFePO4 can be by Li
xfe
1-yl
ypO
4represent, the chemical formula of this Li, Ni, Mn oxide can be by Li
xni
0.5+z-amn
1.5-z-bl
ar
bo
4represent, the chemical formula of this lithium nickel cobalt manganese oxide can be by Li
xni
cco
dmn
el
fo
2represent, 0.1≤x≤1.1 wherein, 0≤y<1,0≤z<1.5,0≤a-z<0.5,0≤b+z<1.5,0<c<1,0<d<1,0<e<1,0≤f≤0.2, c+d+e+f=1.L and R are selected from one or more in alkali metal, alkali earth metal, 13 family element, 14 family element, transition element and rare earth element, preferably, L and R are selected from least one in Mn, Ni, Cr, Co, V, Ti, Al, Fe, Ga, Nd and Mg.
The particle diameter of this lithium-transition metal oxide positive electrode active materials can be 20nm to 10 μ m.Preferably, the particle diameter of this metallic particles is less than the particle diameter of this lithium-transition metal oxide positive electrode active materials, so that this metallic particles can be fully and the Surface Contact of this lithium-transition metal oxide positive electrode active materials, thereby be more conducive in follow-up sintering process this metal fluoride at the forming core of this lithium-transition metal oxide surface of positive electrode active material.Preferably, the particle diameter of this lithium-transition metal oxide positive electrode active materials is 10 to 500 times of this metallic particles particle diameter.More preferably, the particle diameter of this lithium-transition metal oxide positive electrode active materials is 100 to 500 times of this metallic particles particle diameter.
In step S32, as long as the hybrid mode that this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials are mixed can make this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials mix.This metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials can mix at normal temperatures.Preferably, this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials can mix in inert atmosphere.Preferably, this fluorine-containing non-oxygen compound can be solid, this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials can be taked the method for grinding or ball milling to mix.Preferably, this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials adopt the method for ball milling to mix, adopt the method for ball milling can not only make this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials mix, also can further reduce the particle diameter of this metallic particles, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials, more be conducive to the carrying out of sintering reaction in follow-up sintering process.
The quality of this lithium-transition metal oxide positive electrode active materials can be 50% to 99% of the 3rd mixture quality.Preferably, the quality of this lithium-transition metal oxide positive electrode active materials can be 80% to 99% of the 3rd mixture quality.More preferably, the quality of this lithium-transition metal oxide positive electrode active materials can be 90% to 97% of the 3rd mixture quality.Lithium-transition metal oxide positive electrode active materials in this mass range can guarantee that the coated lithium-transition metal oxide positive electrode active materials of this metal fluoride has good conductivity, can make again contacting of effectively isolated this lithium-transition metal oxide positive electrode active materials of coated metal fluoride layer and electrolyte.
In step S33, the temperature of described sintering is for making this fluorine-containing non-oxygen compound that the temperature of decomposing can occur.In the present embodiment, the condition of described sintering is identical with the sintering condition of first embodiment of the invention.
In step S33, in described sintering process, this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas, this metallic particles and the reaction of this hydrogen fluoride gas generate metal fluoride, this metal fluoride carries out forming core at this lithium-transition metal oxide surface of positive electrode active material, and growth gradually, finally formed the coated lithium-transition metal oxide positive electrode active materials of metal fluoride.
The metal fluoride layer of lithium-transition metal oxide positive electrode active materials that this metal fluoride is coated is even continuous coating layer.The thickness of this metal fluoride layer can regulate and control by the ratio of this metallic particles in the 3rd mixture and this fluorine-containing non-oxygen compound.Preferably, the thickness of this metal fluoride layer can be 0.2nm to 50nm, metal fluoride layer in this thickness range, when guaranteeing this lithium-transition metal oxide positive electrode active materials conductivity, can effectively completely cut off contacting of this lithium-transition metal oxide positive electrode active materials and electrolyte.More preferably, the metal fluoride coating thickness of the coated lithium-transition metal oxide positive electrode active materials of this metal fluoride is 1nm to 5nm.
Further, when this fluorine-containing non-oxygen compound is fluorine-containing during without oxygen organic, because this is fluorine-containing, without oxygen organic, can in described sintering process, decomposite carbon clusters, this carbon clusters can be adsorbed on this metal fluoride layer surface, on this metal fluoride layer surface, form carbon-coating, thereby the hud typed positive electrode that forms a three-decker, this hud typed positive electrode is followed successively by lithium-transition metal oxide positive electrode active materials, metal fluoride layer and carbon-coating from inside to outside.Existence due to this metallic particles in described sintering process, in the process that forms carbon-coating, can there is graphitization in this carbon clusters, therefore the carbon-coating of this hud typed positive electrode is graphitization carbon-coating, this graphitization carbon-coating can provide space and the more electron transport passage of more volumetric expansion and contraction for this hud typed positive electrode, can make this hud typed positive electrode have better electric conductivity.
Third embodiment of the invention adopts the method for directly carrying out sintering at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride, the method not only simple to operate, cost is lower, be applicable to suitability for industrialized production, and the thickness of this metal fluoride layer is controlled, this metal fluoride layer can effectively completely cut off contacting of lithium-transition metal oxide positive electrode active materials and electrolyte, prevents lithium ion battery performance degradation in use.
Third embodiment of the invention is carried out sintering after also described metallic compound, described fluorine-containing non-oxygen compound and described lithium-transition metal oxide positive electrode active materials can being mixed and is prepared the coated lithium-transition metal oxide positive electrode active materials of metal fluoride, can there is decompose to generate metallic particles in this metallic compound, thereby provide the metallic particles that particle diameter is less for the preparation of the coated lithium-transition metal oxide positive electrode active materials of metal fluoride in described sintering process.
Refer to Fig. 4, fourth embodiment of the invention further provides a kind of preparation method at described lithium-transition metal oxide surface of positive electrode active material clad metal fluoride, comprising:
S41, provides described metallocene, described fluorine-containing non-oxygen compound and described lithium-transition metal oxide positive electrode active materials;
S42, is mixed to get a 4 mixture by this metallocene, this fluorine-containing non-oxygen compound and this lithium-transition metal oxide positive electrode active materials; And
S43 carries out sintering by this 4 mixture in inert atmosphere, obtains the coated lithium-transition metal oxide positive electrode active materials of metal fluoride.
In step S42, the hybrid mode of described mixing is identical with the hybrid mode of mixing in third embodiment of the invention.The quality of this lithium-transition metal oxide positive electrode active materials can be 50% to 99% of this 4 mixture quality.Preferably, the quality of this lithium-transition metal oxide positive electrode active materials can be 80% to 99% of this 4 mixture quality.More preferably, the quality of this lithium-transition metal oxide positive electrode active materials can be 90% to 97% of this 4 mixture quality.Lithium-transition metal oxide positive electrode active materials in this mass range can guarantee that the coated lithium-transition metal oxide positive electrode active materials of this metal fluoride has good conductivity, can make again contacting of effectively isolated this lithium-transition metal oxide positive electrode active materials of coated metal fluoride layer and electrolyte.
In step S43, the condition of described sintering is identical with the sintering condition of first embodiment of the invention.
In step S43, this metallocene occurs to decompose and generates metal simple-substance, and this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas, and this metal simple-substance and the reaction of this hydrogen fluoride gas generate metal pentafluoride composition granule.Because the boiling point of this metallocene is lower, in described sintering process, this metallocene can distil as gas and be evenly distributed in this positive electrode active materials around, therefore, finally can form evenly continuous metal fluoride coating layer at this surface of positive electrode active material.
The thickness of this metal fluoride layer can regulate and control by the ratio of this metallocene in this 4 mixture and this fluorine-containing non-oxygen compound.Preferably, the thickness of this metal fluoride layer can be 0.2nm to 50nm, metal fluoride layer in this thickness range, when guaranteeing this lithium-transition metal oxide positive electrode active materials conductivity, can effectively completely cut off contacting of this lithium-transition metal oxide positive electrode active materials and electrolyte.More preferably, the metal fluoride coating thickness of the coated lithium-transition metal oxide positive electrode active materials of this metal fluoride is 1nm to 5nm.
Further, can also Formed cluster after this metallocene decomposes, the surface that this carbon clusters can be adsorbed onto this metal fluoride coating layer forms carbon coating layer, finally formed the hud typed positive electrode of three-decker, this hud typed positive electrode is followed successively by lithium-transition metal oxide positive electrode active materials, metal fluoride and carbon-coating from inside to outside.Existence due to this metal simple-substance in described sintering process, in the process that forms carbon-coating, can there is graphitization in this carbon clusters, therefore the carbon-coating of this hud typed positive electrode is graphitization carbon-coating, this graphitization carbon-coating can provide space and the more electron transport passage of more volumetric expansion and contraction for this hud typed positive electrode, can make this hud typed positive electrode have better electric conductivity.
Fourth embodiment of the invention adopts the method for directly carrying out sintering at lithium-transition metal oxide surface of positive electrode active material clad metal fluoride, can generate evenly continuous coating layer at this lithium-transition metal oxide surface of positive electrode active material, the method not only simple to operate, cost is lower, be applicable to suitability for industrialized production, and the thickness of this metal fluoride layer is controlled, this metal fluoride layer can effectively completely cut off contacting of lithium-transition metal oxide positive electrode active materials and electrolyte, prevents lithium ion battery performance degradation in use.
Embodiment 1
Ferrocene and PVDF are mixed according to fluorine/ferro element mol ratio 2:1 ratio, with 500rpm/min speed ball milling, within 2 hours, obtain one first mixture.This first mixture is placed in to rustless steel container, container is placed in to glove box applying argon gas, then this first mixture is reacted 5 hours under 600 ° of C, obtain the coated ferrous fluoride of carbon.
Refer to Fig. 5, the coated ferrous fluoride of this carbon is rod-shpaed particle, the length of this rod-shpaed particle approximately 1 μ m, and width is between the μ m of 100nm ~ 1, and carbon-coating thickness is about 20nm.Refer to Fig. 6, the diffraction maximum of XRD collection of illustrative plates of this product and the diffraction maximum of the standard diagram of ferrous fluoride are consistent, prove that above-mentioned preparation method can prepare pure phase and the good ferrous fluoride of degree of crystallinity.Refer to Fig. 7, the carbon-coating of the coated ferrous fluoride of this carbon has lattice fringe, and fringe spacing is 0.34nm, conforms to the interlamellar spacing of graphite, proves that the carbon-coating of the coated ferrous fluoride of this carbon is graphitization carbon-coating.When being used for to lithium ion cell positive, the coated ferrous fluoride of this carbon there is 300mAhg
-1lithium storage content first, coulomb efficiency is more than 96%, the capacitance loss rate at every turn circulating within 50 times that circulate is 0.66%.
Embodiment 2
By ferrocene and NH
4f mixes than 2.05:1 ratio according to fluorine/ferro element, with 400rpm/min speed ball milling, within 1 hour, obtains one first mixture.This first mixture is placed in to rustless steel container, container is placed in to glove box inflated with nitrogen, then by this first mixture in 650 ° of C reaction hour, obtain the coated ferrous fluoride of carbon.
Refer to Fig. 8, the coated ferrous fluoride of this carbon is spheric granules, and this spherical particle diameters is between the μ m of 100nm ~ 1, and carbon-coating thickness is about 10nm.When the coated ferrous fluoride of this carbon is used for to lithium ion cell positive, there is 330mAhg
-1lithium storage content first, coulomb efficiency is more than 95%, and the capacitance loss rate of the each circulation within 40 times that circulates is 0.72%, refers to Fig. 9, the coated ferrous fluoride of this carbon is compared with the ferrous fluoride of carbon coated not, has better coulombic efficiency and more stable cycle performance.
Embodiment 3
By cobaltocene and NH
4hF
2according to fluorine/carbon, than 1.95:1 ratio, mix, be ground to mix and obtain one first mixture.This first mixture is placed in to rustless steel container, container is placed in to glove box and fills helium, then 550 ° of C reactions 4 hours, obtain the coated manganous fluoride of carbon.
The coated manganous fluoride of this carbon is spheric granules, and this spherical particle diameters is between the μ m of 50nm ~ 0.5, and carbon-coating thickness is about 15nm.When the coated manganous fluoride of this carbon is used for lithium ion cell positive, there is 380mAhg
-1lithium storage content first, coulomb efficiency is more than 95%, the capacitance loss rate at every turn circulating within 80 times that circulate is 0.52%.
Embodiment 4
The iron particle of 50nm and PVDF are mixed according to fluorine/ferro element mol ratio 2:1 ratio, with 500rpm/min speed ball milling, within 2 hours, obtain one second mixture.This second mixture is placed in to rustless steel container, container is placed in to glove box applying argon gas, then this second mixture is reacted 5 hours under 600 ° of C, obtain the coated ferrous fluoride of carbon.When being used for to lithium ion cell positive, the coated ferrous fluoride of this carbon there is 300mAhg
-1lithium storage content first, coulomb efficiency is more than 96%, the each capacitance loss rate within 50 times that circulates is 0.66%.
Embodiment 5
The iron particle of 100nm, PVDF and cobalt acid lithium are mixed, with 500rpm/min speed ball milling, within 2 hours, obtain one the 3rd mixture, in this iron particle and this PVDF, the mol ratio of fluorine/ferro element is 2:1, and the quality of this cobalt acid lithium is 80% of the 3rd mixture quality.The 3rd mixture is placed in to rustless steel container, container is placed in to glove box applying argon gas, then the 3rd mixture is reacted 5 hours under 600 ° of C, obtain the shell-nuclear compounded structure of the coated cobalt acid lithium of ferrous fluoride.When the shell-nuclear compounded structure of the coated cobalt acid of this ferrous fluoride lithium is used for to lithium ion cell positive, at 50 times, discharges and recharge after circulation, the coated cobalt acid of ferrous fluoride lithium is at 30 ° of C of room temperature and current density 0.8Ma/cm
2capability retention be 93%.These results have proved, along with the increase of cycle-index, the coated cobalt acid of ferrous fluoride lithium capability retention is higher.
Embodiment 6
By dicyclopentadienyl nickel, NH
4f mixes with cobalt acid lithium, with 400rpm/min speed ball milling, within 1 hour, obtains a 4 mixture.Dicyclopentadienyl nickel and NH in this 4 mixture
4fluorine/nickel element mol ratio of F is 2.05:1, and the quality of cobalt acid lithium is this 4 mixture quality 85%.This 4 mixture is placed in to rustless steel container, container is placed in to glove box inflated with nitrogen, then by this 4 mixture in 650 ° of C reaction hour, obtain hud typed positive electrode, this hud typed positive electrode is respectively cobalt acid lithium, NiF from the inside to surface
2and graphitization carbon-coating.This hud typed positive electrode is applied to lithium ion cell positive, there is 140mAhg
-1lithium storage content first, coulomb efficiency is more than 95%, the capacitance loss rate at every turn circulating within 40 times that circulate is 0.72%.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
1. a preparation method for anode active material of lithium ion battery, comprising:
Metallic particles, fluorine-containing non-oxygen compound and anaerobic carbon source are provided;
This metallic particles, this fluorine-containing non-oxygen compound and this anaerobic carbon source are mixed to get to a mixture; And
This mixture is carried out in inert atmosphere to sintering, obtain carbon-clad metal fluoride, this fluorine-containing non-oxygen compound occurs to decompose and discharges hydrogen fluoride gas in described sintering process.
2. the preparation method of anode active material of lithium ion battery as claimed in claim 1, it is characterized in that, the carbon-coating of this carbon-clad metal fluoride is graphitization carbon-coating, the least significant non-zero valence state m+ that in this carbon-clad metal fluoride, the valence state of metallic element is this metallic element.
3. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, this metallic particles is simple substance, and this metallic particles is a kind of in Ti, V, Mn, Fe, Bi, Co, Ni, Cu, Zn, Sn, Ag, Pb, Ca or Ba particle.
4. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, this fluorine-containing non-oxygen compound is fluorine-containing without oxygen organic.
5. the preparation method of anode active material of lithium ion battery as claimed in claim 4, is characterized in that, this is fluorine-containing is one or more in Kynoar, polytetrafluoroethylene, fluorinated ethylene propylene copolymer and polyvinyl fluoride without oxygen organic.
6. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, this fluorine-containing non-oxygen compound is fluorine-containing anaerobic inorganic matter.
7. the preparation method of anode active material of lithium ion battery as claimed in claim 6, is characterized in that, this fluorine-containing anaerobic inorganic matter is NH
4f and NH
4hF
2in one or more.
8. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, in this metallic particles and this fluorine-containing non-oxygen compound, the stoichiometric proportion of fluorine element and metallic element is (m-0.1): 1 arrives (m+0.1): 1.
9. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, described sintering temperature is 400 to 1000 ° of C, and the time of described sintering is 1 hour to 10 hours.
10. the preparation method of anode active material of lithium ion battery as claimed in claim 1, is characterized in that, described sintering temperature is 600 to 800 ° of C, and the time of described sintering is 2 hours to 5 hours.
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| WO2015172625A1 (en) * | 2014-05-16 | 2015-11-19 | 江苏华东锂电技术研究院有限公司 | Method for preparing active material for positive electrode of lithium-ion battery |
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| CN106207116A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of method of one-step synthesis method ferrous fluoride/C positive electrode material |
| CN111029551A (en) * | 2019-12-23 | 2020-04-17 | 宁波革鑫新能源科技有限公司 | Synthesis of in situ carbon coated FeF2Method for producing granules, and FeF2Particle and battery |
| CN114899371A (en) * | 2022-04-29 | 2022-08-12 | 佛山市德方纳米科技有限公司 | Low-water-content cathode material, preparation method thereof and lithium ion battery |
| CN114899371B (en) * | 2022-04-29 | 2024-03-19 | 深圳市德方纳米科技股份有限公司 | Low-water-content positive electrode material, preparation method thereof and lithium ion battery |
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