CN108336299A - A kind of anode material of lithium battery and preparation method thereof, anode structure and lithium battery - Google Patents

A kind of anode material of lithium battery and preparation method thereof, anode structure and lithium battery Download PDF

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Publication number
CN108336299A
CN108336299A CN201711371078.4A CN201711371078A CN108336299A CN 108336299 A CN108336299 A CN 108336299A CN 201711371078 A CN201711371078 A CN 201711371078A CN 108336299 A CN108336299 A CN 108336299A
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lithium battery
anode
materials
lif
anode material
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CN108336299B (en
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张晓琨
黄楷
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Chengdu Dachao Technology Co.,Ltd.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to technical field of lithium batteries more particularly to a kind of anode material of lithium battery and preparation method thereof.A kind of anode material of lithium battery, the anode material of lithium battery includes composite nano materials, the composite nano materials include carbon nanotube and the LiMNF particles that are formed on the carbon nanotube, and the MN of LiMNF particles can be the alloy composite of CoNi, FeCu, FeCo or other arbitrary two kinds of transition metal.Skeleton of the carbon nanotube as support LiMNF particles, can maintain the structure of the composite nano materials well.In carrying out the cyclic process of high-voltage charge and discharge repeatedly, the space structure of composite nano materials can modulate the composite nano materials volume change in charge and discharge process well, reach the demand of high pressure resistant property and have high specific capacity.

Description

A kind of anode material of lithium battery and preparation method thereof, anode structure and lithium battery
【Technical field】
The present invention relates to technical field of lithium batteries more particularly to a kind of anode material of lithium battery and preparation method thereof.
【Background technology】
Most of traditional lithium ion anode material is insertion and the abjection type chemical combination of the embedding dislocation point of active lithium ion Object (such as one-dimensional tunnel olivine structural, two-dimensional layered structure and three-dimensional spinel structure etc.), such positive electrode is typically only capable to Enough insertions and abjection provided less than or equal to 1mol lithium ions, therefore its specific capacity receives certain limitation.In addition to de- Outside the compound of insert-type reaction mechanism, recently, there is the lithium ion anode material TMaXb (TM of conversion or alloying type mechanism For transition metal, X is often F and S) also by the extensive concern of researcher, wherein FeF3It is studied most, because it is with pole High Theoretical Mass specific capacity 712mAh/g, average voltage 2.75V, energy density are roughly equal to 1950Wh/kg, and energy density is much Higher than traditional anode material of lithium battery.But such fluoride positive electrode is due to the reaction mechanism of its own, in charge and discharge There is the fracture and reconstruction of chemical bond in the process, therefore there is voltage delay, polarization increases, and volume change is big, cyclical stability The shortcomings of poor.Further, since such fluoride itself does not have lithium ion, therefore actually dresses up and need to bear when full battery is applied Pole prelithiation increases certain application cost.
Therefore it is development high power lithium battery key point to find development high-energy density high-voltage anode material.
【Invention content】
To overcome current lithium ion anode material specific capacity not high, the problem for causing existing lithium battery energy density relatively low, The present invention provides a kind of anode material of lithium battery and preparation method thereof with height ratio capacity.
In order to solve the above-mentioned technical problem the present invention, provides a technical solution：A kind of anode material of lithium battery, the lithium battery Positive electrode includes composite nano materials, and the composite nano materials include carbon nanotube and are formed on the carbon nanotube LiMNF particles, the wherein MN in LiMNF particles can be CoNi, FeCu, FeCo or other arbitrary two kinds of transition metal Alloy composite.
Preferably, the particle size of LiMNF particles is in 10nm-30nm ranges, the size of the composite nano materials For 700-1000nm.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of preparation of anode material of lithium battery Method includes the following steps：
Utilize CVD technology synthesizing carbon nanotubes；
MN/LiF composite gel materials are synthesized by chemical synthesis；
MN/LiF composite gel materials are subjected to ultrasonic atomizatio processing；
MN/LiF composite gel materials after atomization are deposited on the carbon nanotube by way of high temperature pyrolysis deposition On, obtain the composite nano materials of packet LiMNF particles.
Preferably, using CVD technology synthesis carbon nanotube length be 700nm or more, internal diameter 1.5-3.0nm, outside Diameter is 3.0-5.0nm.
Preferably, it can be specially solvent-thermal method and collosol and gel to synthesize MN/LiF composite gel materials by chemical synthesis Method.
Preferably, it is preferably sol-gal process by the method that chemical synthesis synthesizes MN/LiF composite gel materials, Step is specific as follows：
By two kinds of transistion metal compound raw materials and LiNO3It is mixed to get raw mixture；
The complex compound that citric acid solution forms three-dimensional net structure is added into raw mixture；
Fluorine raw material is added into complex compound, and is sufficiently stirred to obtain reactant；
Heating reactant obtains MN/LiF composite gel materials.
Preferably, by MN/LiF composite gel materials carry out ultrasonic atomizatio processing the specific steps are：
Supersonic generator and wriggling pumping source are connected, syringe is fixed；
Peristaltic pump is adjusted, setting flow velocity is 6-14ml/h；
Peristaltic pump is opened, setting spraying frequency is that 30-100kHz starts to be atomized.
Preferably, the spraying frequency is preferably 70kHz.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of anode structure, anode knot include Plus plate current-collecting body and it is formed in the anode with regard to the anode thin film on fluid, the anode thin film includes described above compound receives Rice material.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of lithium battery, the lithium battery anode Structure, electrolyte layer and negative pole structure.
Compared with the existing technology, the composite nano materials include carbon nanotube and are formed on the carbon nanotube LiMNF particles, for the particle size of LiMNF particles in 10nm-30nm ranges, the size of the composite nano materials is 700- 1000nm.Described composite nano materials itself have lithium ion, and lithium battery anode knot is applied to as positive electrode active materials On structure, the processing of prelithiation need not be carried out again, can be applied directly on lithium battery anode structure, enhance in fact With property, reduce processing cost.
In addition, skeleton of the carbon nanotube as support LiMNF particles, can maintain the knot of the composite nano materials well Structure.In carrying out the cyclic process of high-voltage charge and discharge repeatedly, the space structure of composite nano materials can modulate charge and discharge well The volume change of composite nano materials in the process reaches the demand of high pressure resistant property.
Further, carbon nanotube is nano-grade size, and LiMNF particles are all nano-scale rank, and LiMNF particles exist It is distributed under nano-scale around porous carbon nanotube so that the conductivity of the carbon composite nano-material of formation has obtained substantially The phenomenon that being promoted, slowing down in charge and discharge process polarization and voltage delay, raising electric conductivity and specific capacity.
Length using the carbon nanotube of CVD technology synthesis is 700nm or more, internal diameter 1.5-3.0nm, outer diameter 3.0- 5.0nm.The size range for controlling carbon nanotube, with preferably so that the size of composite nano materials is in Nano grade range.
It is preferably sol-gal process, sol-gal process by the method that chemical synthesis synthesizes MN/LiF composite gel materials MN/LiF complex sol materials can be first obtained during synthesis MN/LiF composite gel materials, form MN/LiF plural gel materials Temperature is relatively low during the entire process of material, and reaction relatively mitigates so that the crosslinking of finally obtained MN/LiF complex sols material Structure is more stable.
Frequency of spraying during MN/LiF composite gel materials are carried out ultrasonic atomizatio processing is preferably 70kHz, can be very The rate of good guarantee atomization MN/LiF complex sol materials, while making the MN/LiF complex sol scantlings after atomization full Foot requires.
Anode knot includes plus plate current-collecting body and is formed in the anode with regard to the anode thin film on fluid, the anode thin film packet Containing composite nano materials described above.Described composite nano materials itself have lithium ion, as positive electrode active materials It is applied on anode structure, the processing of prelithiation need not be carried out again, can be applied directly on anode structure, enhance The practicality reduces processing cost.
The lithium battery includes anode structure, electrolyte layer and negative pole structure described above.
Skeleton of the carbon nanotube as support LiMNF particles, can maintain the structure of the composite nano materials well.When this It is compound in cyclic process of the conductive lithium ion in high-voltage charge and discharge repeatedly when composite nano materials are applied in lithium-ion electric The space structure of nano material can modulate the variation of anode structure volume in charge and discharge process well, avoid collapsing for anode structure It falls into so that lithium battery has the characteristic of high voltage, to improve the energy density of lithium battery.Further, carbon nanotube is Nano-scale dimension, while LiMNF particles are all nano-scale rank, LiMNF particles are distributed in porous carbon under nano-scale Around nanotube so that the conductivity of the composite nano materials of formation is significantly enhanced, and slows down lithium battery in charge and discharge Polarization and the phenomenon that voltage delay in journey, improves the electric conductivity and energy density of lithium battery.
【Description of the drawings】
Fig. 1 is the microstructure schematic diagram of composite nano materials in the present invention；
Fig. 2 is the flow chart that composite nano materials are prepared in the present invention；
Fig. 3 is the equipment flowsheet that composite nano materials are prepared in the present invention；
Fig. 4 is the flow chart of synthesizing carbon nanotubes in the present invention；
Fig. 5 is the flow chart of solvent structure MN/LiF composite gel materials in the present invention；
Fig. 6 is the flow chart that sol-gal process synthesizes MN/LiF composite gel materials in the present invention；
Fig. 7 is the flow chart for being atomized MN/LiF composite gel materials in the present invention；
Fig. 8 is the overall structure diagram of anode structure in the present invention；
Fig. 9 is the overall structure diagram of lithium battery structure in the present invention.
【Specific implementation mode】
It is with reference to the accompanying drawings and embodiments, right in order to make the purpose of the present invention, technical solution and advantage be more clearly understood The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
Referring to Fig. 1, a kind of anode material of lithium battery, which includes composite nano materials 10, described Composite nano materials 10 include carbon nanotube 101 and the LiMNF particles 102, LiMNF being formed on the carbon nanotube 101 MN in particle 102 can be the alloy composite of CoNi, FeCu, FeCo or other arbitrary two kinds of transition metal.
Wherein the particle size of LiMNF particles 102 is in 10nm-30nm ranges, the size of the composite nano materials 10 700-1000nm。
The composite nano materials 10 itself have lithium ion, and lithium battery anode is applied to as positive electrode active materials In structure, the processing of prelithiation need not be carried out again, can be applied directly on lithium battery anode structure, enhance it Practicability reduces processing cost.
In addition, skeleton of the carbon nanotube 101 as support LiMNF particles 102, can maintain the composite nano materials well 10 structure.In carrying out the cyclic process of high-voltage charge and discharge repeatedly, the spatial skeleton structure of composite nano materials 10 can be very well Modulation charge and discharge process in 10 volume change of composite nano materials, reach the demand of high pressure resistant property.
Further, carbon nanotube 101 is nano-scale dimension, while LiMNF particles 102 are all nano-scale rank, LiMNF particles 102 are distributed under nano-scale around porous carbon nanotube 101 so that the composite nano materials 10 of formation Conductivity the phenomenon that being significantly enhanced, slowing down in charge and discharge process polarization and voltage delay, improve electric conductivity with Specific capacity.
2 and Fig. 3 are please referred to, the second object of the present invention provides a kind of preparation method of anode material of lithium battery, including such as Lower step：
A1：Utilize CVD technology synthesizing carbon nanotubes 101；
A2：MN/LiF composite gel materials are synthesized by chemical synthesis；
A3：MN/LiF composite gel materials are subjected to ultrasonic atomizatio processing；
A4：MN/LiF composite gel materials after atomization are deposited on the carbon nanometer by way of high temperature pyrolysis deposition On pipe 101, obtain include LiMNF particles 102 composite nano materials 10.
Fig. 3 and Fig. 4 are please referred to, the specific steps of the carbon nanotube 101 of CVD technology synthesis are utilized in above-mentioned steps A1 such as Under：
A11：Carbon source is passed through in tube furnace, flow 10sccm；
A12：It is used as protection gas, flow 120sccm by argon gas；
A13：It is 550-600 DEG C to adjust depositing temperature, and 20-30min is deposited under normal pressure.
In above-mentioned steps A11, before carbon source is passed through tube furnace, transition metal element iron, cobalt, nickel are added into tube furnace And its compound is as catalyst.The carbon source being passed through in the step is C2H2Or CH4Any one of.
After terminating by above-mentioned steps A13 depositions, the length of the carbon nanotube 101 obtained is 700nm or more, internal diameter For 1.5-3.0nm, outer diameter 3-5nm.
It can be specific referring to Fig. 5, synthesizing the MN/LiF composite gel materials by chemical synthesis in above-mentioned steps A2 For solvent-thermal method, any one of sol-gal process.The step of using solvent structure MN/LiF composite gel materials, is specific It is as follows：
A21：The organic solvents such as ethyl alcohol are added into beaker；
A22：Reaction raw materials are added into beaker, and are uniformly mixing to obtain mixed solution；
A23：Mixed solution is transferred in reaction kettle, isothermal reaction obtains MN/LiF composite gel materials.
In above-mentioned steps A22, into beaker, addition reaction raw materials have：
Transition metal raw material：Fe(NO3)3、Cu(NO3)2、Co(NO3)2Or arbitrary two in other transistion metal compounds Kind；
Fluorine raw material：NH4F、NH4HF2Any one of or two kinds；
Lithium ion raw material is：LiNO3
In above-mentioned steps A23, the temperature of isothermal reaction is：120-140 DEG C, the time of isothermal reaction is：8-12h.
Referring to Fig. 6, the step of synthesizing MN/LiF composite gel materials using sol-gal process is specific as follows：
A24：By two kinds of transistion metal compound raw materials and LiNO3It is mixed to get raw mixture；
A25：The complex compound that citric acid solution forms three-dimensional net structure is added into raw mixture；
A26：Fluorine raw material is added into complex compound, and is sufficiently stirred to obtain reactant；
A27：Heating reactant obtains MN/LiF composite gel materials.
In above-mentioned steps A24, transistion metal compound raw material is Fe (NO3)3、Cu(NO3)2、Co(NO3)2Or other mistakes Cross arbitrary two kinds in metallic compound.
In above-mentioned steps A26, fluorine raw material is：NH4F、NH4HF2Any one of or two kinds.
In above-mentioned steps A27, reactant first is heated under the conditions of 60-80 DEG C, obtains MN/LiF complex sol materials, then It is heated under the conditions of 100-120 DEG C again, finally obtains MN/LiF composite gel materials.
In the method for above-mentioned synthesis MN/LiF complex sol materials, preferably sol-gal process is closed using sol-gal process During MN/LiF composite gel materials, reactant first is heated under the conditions of 60-80 DEG C of lower temperature, it is multiple to obtain MN/LiF Sol material is closed, temperature is then increased again, obtains MN/LiF composite gel materials, entire reaction process is slowly mild so that shape At MN/LiF composite gel materials cross-linked structure it is more stable.
It please join in conjunction with Fig. 3 and Fig. 7, MN/LiF composite gel materials are carried out to the tool of ultrasonic atomizatio processing in above-mentioned steps A3 Body process is as follows：
A31：Supersonic generator and wriggling pumping source are connected, syringe is fixed；
A32：Peristaltic pump is adjusted, setting flow velocity is 6-14ml/h；
A33：Peristaltic pump is opened, setting spraying frequency is that 30-100kHz starts to be atomized.
It is the MN/LiF composite gel materials after 30-100kHz makes atomization by set of frequency of spraying in above-mentioned steps A33 Average grain diameter be：10-50μm.
Preferably, spraying set of frequency is 70kHz, can ensure spray rate well under the injection frequency, make simultaneously The average grain diameter of MN/LiF composite gel materials after must being atomized is 30 μm.
While opening peristaltic pump starts atomization, by inert gas Ar, by the MN/LiF complex sol materials after atomization Material strip enters in tube furnace.
It is ultrasound atomization system that MN/LiF composite gel materials, which are carried out the equipment that ultrasonic atomizatio processing uses, passes through ultrasound Wave fog-spray nozzle nebulizes the conversion of gelatinous MN/LiF composite gel materials, with traditional dependence pressure and high-speed motion by liquid Body is ground into short grained fog-spray nozzle difference, and ultrasonic atomization head is to carry out liquid mist using lower ultrasonic vibratory energy Change.Liquid can be transmitted to ultrasonic atomization head by its own gravity or low pressure liquid pump and realize that continuously or discontinuously property is atomized. In the case of limit, liquid atomization quantity is only determined by the working frequency of the conveying capacity of liquid and ultrasonic atomization head.It is logical In the case of often, ultrasonic atomization head working frequency more high atomization processing capacity is lower.The minimum atomization quantity of liquid is up to 1 μ l/ min。
Therefore, the granular size of the MN/LiF composite gel materials after capable of ensureing atomization well is handled by ultrasonic atomizatio Within the scope of 10nm-30nm, preferably to ensure that the size of composite nano materials 10 meets the size requirement of Nano grade.
The MN/LiF composite gel materials after atomization are deposited on by way of high temperature pyrolysis deposition in above-mentioned steps A4 In the carbon nanotube 101, obtain including that the actual temps of the composite nano materials 10 of LiMNF particles 102 is set as 700- 1500 DEG C, sedimentation time 200-600min.
Referring to Fig. 8, the third object of the present invention provides a kind of anode structure 20, the anode knot 20 includes anode collection Body 201 and the anode thin film 202 being formed on the plus plate current-collecting body 201, the anode thin film 202 include described above answer Close nano material 10.
Referring to Fig. 9, the fourth object of the present invention provides a kind of lithium battery 30, the lithium battery 30 include goal of the invention it Three anode structure 20, electrolyte layer 30 and the negative pole structures 40 provided.
Incorporated by reference to Fig. 1, Fig. 8 and Fig. 9, the composite nano materials 10 itself have lithium ion, as positive-active Material is applied on anode structure 20, need not be carried out the processing of prelithiation again, can be applied directly to anode structure 20 On, the practicality is enhanced, processing cost is reduced.
In addition, skeleton of the carbon nanotube 101 as support LiMNF particles 102, can maintain the composite nano materials well 10 structure.When the composite nano materials 10 are applied in lithium-ion electric 30, when conductive lithium ion is in high-voltage charge and discharge repeatedly Cyclic process in, the volume that the spatial skeleton structures of composite nano materials 10 can modulate composite nano materials 10 well becomes Change, avoid collapsing for anode structure 20 so that lithium battery 30 has the characteristic of high voltage, to which the energy for improving lithium battery 30 is close Degree.
Further, carbon nanotube 101 is nano-scale dimension, while LiMNF particles 102 are all nano-scale rank, LiMNF particles 102 are distributed under nano-scale around porous carbon nanotube 101 so that the composite nano materials 10 of formation Conductivity be significantly enhanced, slow down lithium battery 30 and polarize in charge and discharge process and the phenomenon that voltage delay, improve lithium The electric conductivity and energy density of battery 30.
Compared with the existing technology, the composite nano materials include carbon nanotube and are formed on the carbon nanotube LiMNF particles, for the particle size of LiMNF particles in 10nm-30nm ranges, the size of the composite nano materials is 700- 1000nm.Described composite nano materials itself have lithium ion, and lithium battery anode knot is applied to as positive electrode active materials On structure, the processing of prelithiation need not be carried out again, can be applied directly on lithium battery anode structure, enhance in fact With property, reduce processing cost.
In addition, skeleton of the carbon nanotube as support LiMNF particles, can maintain the knot of the composite nano materials well Structure.In carrying out the cyclic process of high-voltage charge and discharge repeatedly, the space structure of composite nano materials can modulate charge and discharge well The volume change of composite nano materials in the process reaches the demand of high pressure resistant property.
Further, carbon nanotube is nano-grade size, and LiMNF particles are all nano-scale rank, and LiMNF particles exist It is distributed under nano-scale around porous carbon nanotube so that the conductivity of the carbon composite nano-material of formation has obtained substantially The phenomenon that being promoted, slowing down in charge and discharge process polarization and voltage delay, raising electric conductivity and specific capacity.
Length using the carbon nanotube of CVD technology synthesis is 700nm or more, internal diameter 1.5-3.0nm, outer diameter 3.0- 5.0nm.The size range for controlling carbon nanotube, with preferably so that the size of composite nano materials is in Nano grade range.
It is preferably sol-gal process, sol-gal process by the method that chemical synthesis synthesizes MN/LiF composite gel materials MN/LiF complex sol materials can be first obtained during synthesis MN/LiF composite gel materials, form MN/LiF plural gel materials Temperature is relatively low during the entire process of material, and reaction relatively mitigates so that the crosslinking of finally obtained MN/LiF complex sols material Structure is more stable.
Frequency of spraying during MN/LiF composite gel materials are carried out ultrasonic atomizatio processing is preferably 70kHz, can be very The rate of good guarantee atomization MN/LiF complex sol materials, while making the MN/LiF complex sol scantlings after atomization full Foot requires.
Anode knot includes plus plate current-collecting body and is formed in the anode with regard to the anode thin film on fluid, the anode thin film packet Containing composite nano materials described above.Described composite nano materials itself have lithium ion, as positive electrode active materials It is applied on anode structure, the processing of prelithiation need not be carried out again, can be applied directly on anode structure, enhance The practicality reduces processing cost.
The lithium battery includes anode structure, electrolyte layer and negative pole structure described above.
Skeleton of the carbon nanotube as support LiMNF particles, can maintain the structure of the composite nano materials well.When this It is compound in cyclic process of the conductive lithium ion in high-voltage charge and discharge repeatedly when composite nano materials are applied in lithium-ion electric The space structure of nano material can modulate the variation of anode structure volume in charge and discharge process well, avoid collapsing for anode structure It falls into so that lithium battery has the characteristic of high voltage, to improve the energy density of lithium battery.Further, carbon nanotube is Nano-scale dimension, while LiMNF particles are all nano-scale rank, LiMNF particles are distributed in porous carbon under nano-scale Around nanotube so that the conductivity of the composite nano materials of formation is significantly enhanced, and slows down lithium battery in charge and discharge Polarization and the phenomenon that voltage delay in journey, improves the electric conductivity and energy density of lithium battery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention Any modification made by within then, equivalent replacement and improvement etc. should all include within protection scope of the present invention.

Claims (10)

1. a kind of anode material of lithium battery, it is characterised in that：The anode material of lithium battery includes composite nano materials, described compound Nano material includes carbon nanotube and the LiMNF particles that are formed on the carbon nanotube, and wherein the MN in LiMNF particles can Think the alloy composite of CoNi, FeCu, FeCo or other arbitrary two kinds of transition metal.
2. anode material of lithium battery as described in claim 1, it is characterised in that：The particle size of LiMNF particles is in 10nm- The size of 30nm ranges, the composite nano materials is 700-1000nm.
3. a kind of preparation method of anode material of lithium battery, which is characterized in that include the following steps：
Utilize CVD technology synthesizing carbon nanotubes；
MN/LiF composite gel materials are synthesized by chemical synthesis；
MN/LiF composite gel materials are subjected to ultrasonic atomizatio processing；
MN/LiF composite gel materials after atomization are deposited on the carbon nanotubes by way of high temperature pyrolysis deposition, are obtained To the composite nano materials of packet LiMNF particles.
4. the preparation method of anode material of lithium battery as claimed in claim 3, it is characterised in that：Utilize CVD technology synthesis The length of carbon nanotube is 700nm or more, internal diameter 1.5-3.0nm, outer diameter 3.0-5.0nm.
5. the preparation method of anode material of lithium battery as claimed in claim 3, it is characterised in that：It is synthesized by chemical synthesis MN/LiF composite gel materials can be specially solvent-thermal method and sol-gal process.
6. the preparation method of anode material of lithium battery as claimed in claim 5, it is characterised in that：It is synthesized by chemical synthesis The method of MN/LiF composite gel materials is preferably sol-gal process, and step is specific as follows：
By two kinds of transistion metal compound raw materials and LiNO3It is mixed to get raw mixture；
The complex compound that citric acid solution forms three-dimensional net structure is added into raw mixture；
Fluorine raw material is added into complex compound, and is sufficiently stirred to obtain reactant；
Heating reactant obtains MN/LiF composite gel materials.
7. the preparation method of anode material of lithium battery as claimed in claim 3, it is characterised in that：By MN/LiF plural gel materials Material carry out ultrasonic atomizatio processing the specific steps are：
Supersonic generator and wriggling pumping source are connected, syringe is fixed；
Peristaltic pump is adjusted, setting flow velocity is 6-14ml/h；
Peristaltic pump is opened, setting spraying frequency is that 30-100kHz starts to be atomized.
8. the preparation method of anode material of lithium battery as claimed in claim 6, it is characterised in that：The spraying frequency is preferably 70kHz。
9. a kind of anode structure, it is characterised in that：The anode knot includes plus plate current-collecting body and is formed in the plus plate current-collecting body On anode thin film, the anode thin film include institute's claim 1-2 any one of them composite nano materials.
10. a kind of lithium battery, it is characterised in that：The lithium battery includes anode structure as claimed in claim 9.
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Citations (4)

* Cited by examiner, † Cited by third party
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