CN107732198A - A kind of copper aluminium silicon Nanoalloy material covers carbon processing method and its application - Google Patents

A kind of copper aluminium silicon Nanoalloy material covers carbon processing method and its application Download PDF

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CN107732198A
CN107732198A CN201710939182.2A CN201710939182A CN107732198A CN 107732198 A CN107732198 A CN 107732198A CN 201710939182 A CN201710939182 A CN 201710939182A CN 107732198 A CN107732198 A CN 107732198A
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copper
silicon
aluminium
parts
nanoalloy
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王宥宏
刘忆恩
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Shanxi Voight Alzheimer New Material Polytron Technologies Inc
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Shanxi Voight Alzheimer New Material Polytron Technologies Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46Alloys based on magnesium or aluminium
    • H01M4/463Aluminium based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

A kind of copper aluminium silicon Nanoalloy material of the present invention covers carbon processing method and its application, belong to lithium cell cathode material preparing technical field, overcome the deficiencies in the prior art of the present invention, there is provided it is a kind of using covering carbon processing method processing copper alusil alloy nano material and its application, the technical scheme used for:Described covering after carbon processing method is dried in vacuo after dispensing, melting, powder processed, separation and screening step is carried out, first by dried copper alusil alloy powder:Carbonaceous material:Water is 80 100 the ratio between by weight:1‑2:8 11, then, it is placed in after stirring in vacuum heat treatment furnace and carries out covering carbon processing in 600~800 DEG C of 2~4h of insulation, vacuum≤0.02Pa, finally, cooled to less than 80 DEG C with the furnace and come out of the stove;The composition of described copper aluminium silicon Nanoalloy is by weight:22~70 parts of silicon, 20~70 parts of copper, 0.5~15 part of aluminium, 0~5 part of impurity, particle diameter≤80 μm;The present invention can be widely applied in lithium cell cathode material neck.

Description

A kind of copper-aluminium-silicon Nanoalloy material covers carbon processing method and its application
Technical field
A kind of copper-aluminium-silicon Nanoalloy material of the present invention covers carbon processing method and its application, belongs to lithium ion battery anode material Expect preparing technical field.
Background technology
New material and clean energy resource are all the prior development directions of State-level, and lithium ion battery is in current energy storage technology Most widely used energy storage battery core, it is the target that the whole world is pursued to improve battery core energy storage density, and battery core energy density carries Height depends on the progress of its positive and negative electrode material, but also the both positive and negative polarity collector with lithium ion battery, both positive and negative polarity bond The progress of the material such as agent, electrolyte and barrier film is relevant.
The core of lithium ion battery is positive and negative electrode electrode material, and it directly decides the performance of battery.Energy Density, cycle life, cycle efficieny and security performance are all the key indexs of electrode material.At present, most common business lithium electricity Pond negative material is mainly carbons and silicon-carbon class material, and they have relatively stable cycle performance, higher cycle efficieny and peace The advantages that completely without pollution, but the capacity of carbons material oneself through close to its theoretical capacity(372mAh/g), the potentiality to be exploited of specific capacity It is small;Silicon-carbon class material is the innovation to carbons material, and 3~15% silicon is added in carbons material makes the gram volume of negative material Reach above and below 420mAh, continuing raising gram volume by this method has technology barriers.The theory of pure silicon stores up lithium specific capacity 4200mAh/g, its highest in all elements, it can increase substantially the energy density of battery, but its as negative material Cycle life and cycle efficieny are poor more than carbon material, lithiumation with go lithiumation during Volume Changes it is huge(>300%)It is to lead The main reason for causing its cycle life difference, the poorly conductive of silicon is one of the reason for its cycle efficieny is low, and the specific surface area of silicon is got over Greatly, its cycle efficieny also can be lower.The short problem low with cycle efficieny of cycle life for how effectively solving silicium cathode material is two Big world problem, so far without feasible technical scheme.All do not have in technologies such as silicon nanoparticle coated with carbon, graphene, titaniums Have the problem settled thoroughly, achieve preferable result of study even in laboratory, also have no idea to be applied to reality Border produces.
Currently available technology lithium cell cathode material is nanoscale, substantially unstressed removal process and technique, by the use of silicon as Subject matter when negative material uses:Cycle life is short, and first all efficiency is low and the discharge and recharge time is grown.Alloying component of the present invention is set Meter is unique with heterogeneous microstructure, the rational size distribution of atomization gained alloy powder, can meet coating of lithium-ion battery demand, Aftertreatment technology is carried out simultaneously, eliminates the process of internal stress so that the lithium battery superior performance that the present invention makes, has and follows Ring long lifespan, the characteristics of first all efficiency highs and short discharge and recharge time.
The content of the invention
Overcome the deficiencies in the prior art of the present invention, there is provided one kind handles copper-aluminium-silicon alloys nanometer using carbon processing method is covered Material and its application.
In order to solve the above technical problems, the technical solution adopted in the present invention is:Described carbon processing method of covering is in dispensing, melted Refine, be dried in vacuo after powder processed, separation and screening step after carry out, first by dried copper-aluminium-silicon alloys powder:Contain Carbonizable substance:Water is the ratio between by weight 80-100:1-2:8-11, then, it is placed in after stirring in vacuum heat treatment furnace 600 ~800 DEG C of 2~4h of insulation carry out covering carbon processing, vacuum≤0.02Pa, finally, cool to less than 80 DEG C with the furnace and come out of the stove;
The composition of described copper-aluminium-silicon Nanoalloy is by weight:22~70 parts of silicon, 20~70 parts of copper, aluminium 0.5~ 15 parts, 0~5 part of impurity, particle diameter≤80 μm.
Further, the carbonaceous material or be edible oil, or be starch, or be sucrose.
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:22~27.5 parts of silicon, copper 60 ~70 parts, 0.5~10 part of aluminium, 0~5 part of impurity
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:27.5~32 parts of silicon, copper 58 ~63 parts, 1~11 part of aluminium, 0~5 part of impurity.
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:32~39 parts of silicon, copper 54~ 59 parts, 1~8 part of aluminium, 0~5 part of impurity.
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:37~42 parts of silicon, copper 55~ 62 parts, 4~15 parts of aluminium, 0~3 part of impurity.
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:42~46 parts of silicon, copper 50~ 58 parts, 5~15 parts of aluminium, 0~3 part of impurity.
Further, the composition of described copper-aluminium-silicon Nanoalloy is by weight:50~70 parts of silicon, copper 20~ 40 parts, 0.5~10 part of aluminium, 0~5 part of impurity.
A kind of carbon processing method of covering using copper-aluminium-silicon Nanoalloy material is preparing lithium ion battery negative material Using.
It is a kind of to cover application of the carbon processing method on lithium ion battery is prepared using copper-aluminium-silicon Nanoalloy material.
The present invention has the advantages that compared with prior art:
The method of the present invention includes:Described carbon processing method of covering is laggard in dispensing, melting, powder processed, separation and screening step Carried out after row vacuum drying, first by dried copper-aluminium-silicon alloys powder:Carbonaceous material:Water is the ratio between by weight 80- 100:1-2:8-11, then, it is placed in after stirring in vacuum heat treatment furnace and in 600~800 DEG C of 2~4h of insulation cover at carbon Reason, vacuum≤0.02Pa, finally, cool to less than 80 DEG C with the furnace and come out of the stove;
The composition of described copper-aluminium-silicon Nanoalloy is by weight:22~70 parts of silicon, 20~70 parts of copper, aluminium 0.5~ 15 parts, 0~5 part of impurity, particle diameter≤80 μm.Further, the carbonaceous material or be edible oil, or be starch, or be sucrose.
Described alloy nano-material integrally includes:Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structures in hole Structure, it obtains particle diameter≤80 μm after being atomized and can reach more than 90%.Cover the alloy nano-material internal stress after carbon substantially to disappear Remove, product properties uniformity is preferable.
Alloying component used in the present invention is unique, and silicone content is less than 5% generally in silicon bronze, and Cu-Al- in the present invention The silicone content scope of Si alloys usual silicon bronze use casting rolled plate, bar, so contains about between 50~77% The high alloy of silicon amount is not reported so far.Preliminary search shows, does not find the research and production of Cu-Al-Si alloy powders so far, Therefore it is original achievement in research that the present invention makes Cu-Al-Si alloy powders using atomization the methods of water/gas/ultrasonic.Atomization gained The heterogeneous microstructure of powder is unique, and copper-rich phase is three-dimensional mesh-structured, when Si-rich phase solidifies, be attached to Tong Bi both sides forming core and Growth, the growth morphology of Si-rich phase are determined by the structural form of copper wall, it will usually irregular lamellar structure is grown into, it is single The thickness of side Silicon-rich synusia is in 300nm or so.The more of a large amount of stomatas, shrinkage cavity and porosity, dislocation, room and hole be present in the alloy Defect(ive) structure structure, substantial amounts of contraction cavity, empty mesh and substantial amounts of shrink defects are left in copper-rich grid element center, they Can volumetric expansion of the partial offset silicon in charge and discharge process, copper-rich stereoscopic grid is to control volume of the silicon in charge and discharge process The primary structure collapsed, meanwhile, copper mesh also has good electric conductivity, is advantageous to entering for nano-silicon synusia removal lithium embedded process OK.Aluminium is distributed mainly on micron particles surface, and it both can effectively prevent the oxidation of copper-rich phase, can effectively subtract again short grained Specific surface area, aluminium can be solid-solution in copper-rich phase on a small quantity, so as to improve the mechanical strength of copper-rich grid and elastic deformability.It is another Al-si eutectic can be formed between part aluminium and silicon, is advantageous to the nanosizing of Si-rich phase, therefore can also be observed in microstructure To granular nanometer Si-rich phase, aluminium can also be used as negative material to use, and its theoretical gram volume is 2234mAh/g, therefore to carrying High gram volume also has certain contribution.The powder has high gram volume, high first all efficiency, high stable cycle efficieny and preferably fast Fill effect.In addition, during the powder metallurgy, copper and aluminium have been used, in lithium ion battery, copper foil is used as negative current collector, Aluminium foil is used as plus plate current-collecting body, and actual use proves, copper foil and aluminium foil do not produce bad side reaction, therefore alloying process In, it there will not be side reaction as alloying element using copper and aluminium.
The application being generally heat-treated is hardware, various metal dusts be heat-treated rarely found.Due to The powder is quickly to be solidified to be formed by water atomization, and there is larger quenching stress, the stress inside it can cause lithium ion Circulating battery bad stability, therefore need to be acted upon using appropriate timeliness means, to improve the stability of mealy structure, this And the unique distinction of the present invention.
Design of alloy of the present invention is unique with heterogeneous microstructure, the rational size distribution of atomization gained alloy powder, Coating of lithium-ion battery demand can be met;Tap density approaches with graphite cathode material;Specific surface area only has graphite cathode material Half or so;Gram volume is 1.5~2.8 times of graphite cathode material;First all efficiency of copper alusil alloy powder of the present invention with Graphite it is close.The cycle efficieny of graphite cathode material is with circulating conservation rate about 98%, copper of the present invention-aluminium-silicon alloys powder Cycle efficieny and circulation conservation rate and graphite it is close.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 makes Nanoalloy Fine Texture of Material SEM image.
Fig. 2 is the microstructure SEM image that the embodiment of the present invention 1 makes negative pole level piece.
Fig. 3 is first all charging and discharging curves that the embodiment of the present invention 1 makes lithium battery.
Fig. 4 is the stable circulation charging and discharging curve that the embodiment of the present invention 1 makes lithium battery.
Fig. 5 is the circulation gram volume and efficiency curve that the embodiment of the present invention 1 makes lithium battery.
Fig. 6 is that the embodiment of the present invention 2 makes Nanoalloy Fine Texture of Material SEM image.
Fig. 7 is the microstructure SEM image that the embodiment of the present invention 2 makes negative pole level piece.
Fig. 8 is first all charging and discharging curves that the embodiment of the present invention 2 makes lithium battery.
Fig. 9 is the stable circulation charging and discharging curve that the embodiment of the present invention 2 makes lithium battery.
Figure 10 is the circulation gram volume and efficiency curve that the embodiment of the present invention 2 makes lithium battery.
Figure 11 is that the embodiment of the present invention 3 makes Nanoalloy Fine Texture of Material SEM image.
Figure 12 is the microstructure SEM image that the embodiment of the present invention 3 makes negative pole level piece.
Figure 13 is first all charging and discharging curves that the embodiment of the present invention 3 makes lithium battery.
Figure 14 is the stable circulation charging and discharging curve that the embodiment of the present invention 3 makes lithium battery.
Figure 15 is the circulation gram volume and efficiency curve that the embodiment of the present invention 3 makes lithium battery.
Figure 16 is that the embodiment of the present invention 3 another formula makes Nanoalloy Fine Texture of Material SEM image.
Figure 17 is the microstructure SEM image that another formula of the embodiment of the present invention 3 makes negative pole level piece.
Figure 18 is first all charging and discharging curves that another formula of the embodiment of the present invention 3 makes lithium battery.
Figure 19 is the stable circulation charging and discharging curve that another formula of the embodiment of the present invention 3 makes lithium battery.
Figure 20 is the circulation gram volume and efficiency curve that another formula of the embodiment of the present invention 3 makes lithium battery.
Figure 21 is that the embodiment of the present invention 4 makes Nanoalloy Fine Texture of Material SEM image.
Figure 22 is the microstructure SEM image that the embodiment of the present invention 4 makes negative pole level piece.
Figure 23 is first all charging and discharging curves that the embodiment of the present invention 4 makes lithium battery.
Figure 24 is the stable circulation charging and discharging curve that the embodiment of the present invention 4 makes lithium battery.
Figure 25 is the circulation gram volume and efficiency curve that the embodiment of the present invention 4 makes lithium battery.
Figure 26 is that the embodiment of the present invention 5 makes Nanoalloy Fine Texture of Material SEM image.
Figure 27 is the microstructure SEM image that the embodiment of the present invention 5 makes negative pole level piece.
Figure 28 is first all charging and discharging curves that the embodiment of the present invention 5 makes lithium battery.
Figure 29 is the stable circulation charging and discharging curve that the embodiment of the present invention 5 makes lithium battery.
Figure 30 is the circulation gram volume and efficiency curve that the embodiment of the present invention 5 makes lithium battery.
Figure 31 is that the embodiment of the present invention 6 makes Nanoalloy Fine Texture of Material SEM image.
Figure 32 is the microstructure SEM image that the embodiment of the present invention 6 makes negative pole level piece.
Figure 33 is first all charging and discharging curves that the embodiment of the present invention 6 makes lithium battery.
Figure 34 is the stable circulation charging and discharging curve that the embodiment of the present invention 6 makes lithium battery.
Figure 35 is the circulation gram volume and efficiency curve that the embodiment of the present invention 6 makes lithium battery.
Embodiment
The carbon processing method of covering of the present invention is after being dried in vacuo after dispensing, melting, powder processed, separation and screening step Carry out, first by dried copper-aluminium-silicon alloys powder:Carbonaceous material:Water is the ratio between by weight 80-100:1-2:8-11, Then, it is placed in after stirring in vacuum heat treatment furnace and carries out covering carbon processing, vacuum in 600~800 DEG C of 2~4h of insulation 0.02Pa, finally, cool to less than 80 DEG C with the furnace and come out of the stove;The composition of described copper-aluminium-silicon Nanoalloy is by weight 's:22~70 parts of silicon, 20~70 parts of copper, 0.5~15 part of aluminium, 0~5 part of impurity, particle diameter≤80 μm.Further, it is described carbon containing Material is edible oil, or is starch, or is sucrose.
Described alloy nano-material integrally includes:Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structures in hole Structure, it obtains particle diameter≤80 μm after being atomized and can reach more than 90%.Cover the alloy nano-material internal stress after carbon substantially to disappear Remove, product properties uniformity is preferable.
Embodiment 1:
(1)The dispensing of Cu-Al-Si alloys,
Fine copper is cut into φ 50mm × 100mm bars, adds vacuum drying to pre-process with pickling using preceding, drying temperature control exists 110±5℃;Fine aluminium is cut into the small aluminium sheets of 50mm × 50mm × 30mm, adds vacuum drying to pre-process with pickling using preceding, drying temperature Degree control is at 200 ± 5 DEG C;The lumpiness of metallic silicon is controlled in 5~30mm, and surface impurity is removed using preceding pickling, is then carried out true Sky drying, drying temperature are controlled at 180 ± 5 DEG C.Dispensing gross weight 20Kg, wherein by weight:22~27.5 parts of silicon, copper 60~70 parts, 0.5~10 part of aluminium, 0~5 part of impurity, impurity includes:Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon etc., first add part Silicon, then copper and aluminium are added, then excess silicon is added, begin to warm up.
(2)The smelting of Cu-Al-Si alloys:
According to intermediate frequency furnace technical parameter is selected in table 1, fusing power is gradually increased, smelting time is controlled in 20~40min so that Furnace charge has a preferable mobility into molten state, tapping temperature control 1350 ± 50 DEG C, using argon gas or nitrogen as Inert protective gas, need continuously to lead to protective gas in fusion process, except when feeding, skimming and pouring into a mould, should try one's best makes Burner hearth is in sealing state;In addition, in order to improve production efficiency and reduce cost, logical protective gas, overall process can not be had to yet Without atmosphere protection and sealing burner hearth.
The technical requirements of the intermediate frequency furnace of table 1 are as follows:
Rated power (KW) Primary voltage (V) Inlet wire current (A) Matching transformer (KVA) DC current (A) DC voltage (V) Voltage of intermediate frequency (V) IF-FRE (KHZ) Fusing time(min)
1500~5000 380~660 2400~4560 1800~7500 3000~5700 500~880 750~1300 0.3~4 30~80
(3)The powder by atomization of Cu-Al-Si alloys:
Water atomization pulverization:, can be with when the temperature of liquid metal reaches 1350 ± 50 DEG C, and when alloy has preferable mobility Start water atomization process.Before water atomization process is started, following preparation need to be carried out:Middle packet system should be opened, in making Between bag temperature reach 600 DEG C.Tundish internal diameter of leting slip a remark selects φ 6-14mm, water atomization 300-450Mpa of pressure, works as the above When index meets to require, start to pour into liquid metals into tundish, carry out powder by atomization.
The method that copper-aluminium-silicon alloys powder can be prepared with aerosolization, is carried out in accordance with the following steps:The first step:Open mist Disguise the middle packet system put, tundish internal diameter of leting slip a remark selects 6~14mm of φ;Second step, regulation molten state copper-aluminium-silicon alloys Tapping temperature be 1300~1700 DEG C;3rd step, liquid metal is poured into tundish, aerosolization 10~50MPa of pressure, is entered Promoting the circulation of qi powder by atomization;The source of the gas of described aerosolization is pure air, or is argon gas, or is nitrogen.
The method that ultrasonic aerosolization can also be utilized to prepare copper-aluminium-silicon alloys powder, is carried out in accordance with the following steps:First Step:The middle packet system of atomising device is opened, tundish internal diameter of leting slip a remark selects 6~14mm of φ;Second step, regulation molten state copper- The tapping temperature of aluminium-silicon alloys is 1300~1700 DEG C;3rd step, liquid metal is poured into tundish, adjust supersonic gas The flow velocity of stream is 2~2.5 Mach, and the pulse frequency of supersonic airstream is 80~100KHz, and stream pressure is 10~50Mpa, is entered The ultrasonic gas-atomized powder of row;The source of the gas of described ultrasonic aerosolization is pure air, or is argon gas, or is nitrogen.
The tundish that above-mentioned 3 kinds of methods use, its temperature can be room temperature to 1200 DEG C, can flexibly be adjusted according to actual process Section.
(4)The separation of solid and liquid of alloy powder:
2~3h of standing is needed after atomization, clear water in atomization tank is discharged, takes out collecting tank, press filteration system is opened, uses 6Mpa pressure Compressed air, carry out press filtration separation of solid and liquid, time of filter pressing is not less than 20min.
(5)The screening of alloy powder:
After press filtration terminates, by the pressure discharge ± 0Mpa in collecting tank, collecting tank is opened, powder is taken out, powder is transferred to Bipyramid vacuum drying stove, vavuum pump to be opened, vacuum drying oven negative pressure of vacuum is reached 0.1Mpa, drying oven starts to rotate with 60r/min, Open heating system to be heated, heating-up temperature is reached 180 DEG C.Drying time is 6h, stops heating, continues to rotate, and is cooled down 3h, when powder temperature is down to 80 ± 10 DEG C, nitrogen is filled with to normal pressure, can be with can opening blowing.Material is cooled to normal temperature in an atmosphere.
Screening process is carried out to powder from ultrasonic wave spin vibration sieve, obtaining particle diameter using the mesh of 30 mesh+300 is less than 48 μm Alloy anode powder.
(6)The post processing of alloy powder:
It is the ratio between by weight=80-100 by dried copper-aluminium-silicon alloys powder, carbonaceous material, water:1-2:8-11, preferably Formula be that dried copper-aluminium-silicon alloys powder, carbonaceous material, water are=100 the ratio between by weight:1:9, after stirring It is placed in vacuum heat treatment furnace and carries out covering carbon processing in 600~800 DEG C of 2~4h of insulation, cools to 80 DEG C with the furnace and come out of the stove, it is described to contain Carbonizable substance is edible oil, or is starch, or is sucrose.
The post processing of alloy powder also can be selected electric and magnetic oscillation aging process and carry out Ageing Treatment to powder, and vibration frequency exists Change in the range of 3000~5000Hz, time of vibration needs 24h.
The post processing of alloy powder can also use:Above-mentioned powder is placed into vacuum drying oven and carries out vacuum heat, vacuum Heat treatment temperature is 250~500 DEG C, and the time is 48~90h, vacuum≤0.02Pa.
Table 2 is that the physical parameter of the copper-aluminium-silicon alloys nanometer negative pole powder prepared according to the method described above is as follows:
Fig. 1 is the microstructure SEM image of the embodiment of the present invention 1, and Fig. 2 is that the embodiment of the present invention 1 makes the microcosmic of negative pole level piece SEM image is organized, Fig. 3 is first all charging and discharging curves that the embodiment of the present invention 1 makes lithium battery, and Fig. 4 is that the embodiment of the present invention 1 is done Into the stable circulation charging and discharging curve of lithium battery, Fig. 5 is the circulation gram volume and efficiency song that the embodiment of the present invention 1 makes lithium battery Line.
1-5 can see described alloy nano negative material and integrally include from the graph:Stomata, shrinkage cavity and porosity, dislocation, Room and more defect(ive) structure structures in hole, particle diameter≤80 μm, copper-rich phase are three-dimensional mesh-structured, when Si-rich phase solidifies, are depended on In Tong Bi both sides forming core and growth, the growth morphology of Si-rich phase is determined by the structural form of copper wall, it will usually is grown into and is not advised Lamellar structure then, the thickness of unilateral Silicon-rich synusia is in 300nm or so.A large amount of stomatas, shrinkage cavity and porosity, position be present in the alloy Wrong, room and more defect(ive) structure structures in hole, after making negative pole level piece, it is empty to leave substantial amounts of contraction in copper-rich grid element center Hole, empty mesh and substantial amounts of shrink defects, they can volumetric expansion of the partial offset silicon in charge and discharge process, copper-rich is three-dimensional Grid is the primary structure for controlling volume of the silicon in charge and discharge process to collapse, meanwhile, copper mesh also has good electric conductivity, Be advantageous to the progress of nano-silicon synusia removal lithium embedded process.Aluminium is distributed mainly on micron particles surface, and it both can effectively prevent richness The oxidation of copper phase, it can effectively subtract short grained specific surface area again, aluminium can be solid-solution in copper-rich phase on a small quantity, so as to improve copper-rich net The mechanical strength of lattice and elastic deformability.Al-si eutectic can be formed between another part aluminium and silicon, is advantageous to Si-rich phase Nanosizing, therefore granular nanometer Si-rich phase is can also be observed that in microstructure, aluminium can also be used as negative material to use, it Theoretical gram volume be 2234mAh/g, therefore to improve gram volume also have certain contribution.The powder has high gram volume, Gao Shou All efficiency, high stable cycle efficieny and preferable fast charge effect.In addition, during the powder metallurgy, used copper and aluminium, lithium from In sub- battery, copper foil is used as negative current collector, and aluminium foil is used as plus plate current-collecting body, and actual use proves that copper foil and aluminium foil do not have Have and produce bad side reaction, therefore in alloying process, it there will not be side reaction as alloying element using copper and aluminium.
The rational size distribution of atomization gained alloy powder, can meet coating of lithium-ion battery demand, then cover carbon vacuum Heat treatment so that Nanoalloy internal stress substantially eliminates, and material property uniformity is good;Make lithium ion battery negative material and lithium Ion battery, its tap density approach with graphite cathode material;Specific surface area only has half of graphite cathode material or so;Gram hold Amount is 1.5~2.8 times of graphite cathode material;First all efficiency of copper alusil alloy powder of the present invention and graphite it is close.Graphite The cycle efficieny of negative material about 98%, the cycle efficieny of copper of the present invention-aluminium-silicon alloys powder and is followed with circulation conservation rate Environmentally friendly holdup and graphite it is close.
Embodiment 2, the composition of described copper-aluminium-silicon alloys is by weight:27.5~32 parts of silicon, copper 58~63 Part, 1~11 part of aluminium, 0~5 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1550 ± 50 DEG C, other steps and side Method is substantially similar to embodiment 1, and shown in Fig. 6-10, the performance of its final products of the present embodiment with embodiment 1 is also essentially identical.
Embodiment 3, the composition of described copper-aluminium-silicon alloys is by weight:32~39 parts of silicon, 54~59 parts of copper, 1~8 part of aluminium, 0~5 part of impurity, the tapping temperatures of molten state copper-aluminium-silicon alloys are 1650 ± 50 DEG C, other steps and method with Embodiment 1 is substantially similar, and shown in Figure 11-20, the performance of its final products of the present embodiment with embodiment 1 is also essentially identical.
Embodiment 4, the composition of described copper-aluminium-silicon alloys is by weight:37~42 parts of silicon, 55~62 parts of copper, 4~15 parts of aluminium, 0~3 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1360 ± 50 DEG C, other steps and method Substantially similar to embodiment 1, shown in Figure 21-25, the performance of its final products of the present embodiment with embodiment 1 is also essentially identical.
Embodiment 5, the composition of described copper-aluminium-silicon alloys is by weight:42~46 parts of silicon, 50~58 parts of copper, 5~15 parts of aluminium, 0~3 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1600 ± 50 DEG C, other steps and method Substantially similar to embodiment 1, shown in Figure 26-30, the performance of its final products of the present embodiment with embodiment 1 is also essentially identical.
Embodiment 6, the composition of described copper-aluminium-silicon alloys is by weight:50~70 parts of silicon, 20~40 parts of copper, 0.5~10 part of aluminium, 0~5 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1350 ± 50 DEG C, other steps and side Method is substantially similar to embodiment 1, shown in Figure 31-35, the performances of its final products of the present embodiment with embodiment 1 also basic phase Together.
Above content is to combine the further description that specific preferred embodiment is done to the present invention, it is impossible to is assert The embodiment of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off On the premise of from the present invention, some simple deduction or replace can also be made, should all be considered as belonging to the present invention by being submitted Claims determine scope of patent protection.

Claims (10)

1. a kind of copper-aluminium-silicon Nanoalloy material covers carbon processing method, it is characterised in that:Described carbon processing method of covering is Carried out after being dried in vacuo after dispensing, melting, powder processed, separation and screening step,
First by dried copper-aluminium-silicon alloy nano-powder:Carbonaceous material:Water is the ratio between by weight 80-100:1-2:8-11 Preparation raw material, then, it is placed in after stirring in vacuum heat treatment furnace and carries out covering carbon processing in 600~800 DEG C of 2~4h of insulation, Vacuum≤0.02Pa, finally, cool to less than 80 DEG C with the furnace and come out of the stove;
The composition of described copper-aluminium-silicon Nanoalloy is by weight:22~70 parts of silicon, 20~70 parts of copper, aluminium 0.5~ 15 parts, 0~5 part of impurity, particle diameter≤80 μm.
2. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that:Institute State carbonaceous material or be edible oil, or be starch, or be sucrose.
3. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:22~27.5 parts of silicon, 60~70 parts of copper, 0.5~10 part of aluminium, 0~5 part of impurity
4. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:27.5~32 parts of silicon, 58~63 parts of copper, 1~11 part of aluminium are miscellaneous 0~5 part of matter.
5. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:32~39 parts of silicon, 54~59 parts of copper, 1~8 part of aluminium, impurity 0 ~5 parts.
6. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:37~42 parts of silicon, 55~62 parts of copper, 4~15 parts of aluminium, impurity 0~3 part.
7. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:42~46 parts of silicon, 50~58 parts of copper, 5~15 parts of aluminium, impurity 0~3 part.
8. a kind of copper-aluminium-silicon Nanoalloy material according to claim 1 covers carbon processing method, it is characterised in that institute The composition for the copper-aluminium-silicon Nanoalloy stated is by weight:50~70 parts of silicon, 20~40 parts of copper, 0.5~10 part of aluminium are miscellaneous 0~5 part of matter.
9. a kind of carbon processing method of covering of copper-aluminium-silicon Nanoalloy material using described in claim 1-8 any one is being made The application of standby lithium ion battery negative material.
10. a kind of carbon processing method of covering of copper-aluminium-silicon Nanoalloy material using described in claim 1-8 any one exists Prepare the application on lithium ion battery.
CN201710939182.2A 2017-09-30 2017-09-30 A kind of copper aluminium silicon Nanoalloy material covers carbon processing method and its application Withdrawn CN107732198A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765024A (en) * 2003-03-26 2006-04-26 佳能株式会社 Electrode material for lithium secondary battery and electrode structure having the electrode material
CN101005133A (en) * 2005-11-29 2007-07-25 三星Sdi株式会社 Negative active material for rechargeable lithium battery and rechargeable lithium battery
CN102361073A (en) * 2011-11-02 2012-02-22 北京科技大学 Preparation method of lithium ion battery silicon aluminium carbon composite cathode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765024A (en) * 2003-03-26 2006-04-26 佳能株式会社 Electrode material for lithium secondary battery and electrode structure having the electrode material
CN101005133A (en) * 2005-11-29 2007-07-25 三星Sdi株式会社 Negative active material for rechargeable lithium battery and rechargeable lithium battery
CN102361073A (en) * 2011-11-02 2012-02-22 北京科技大学 Preparation method of lithium ion battery silicon aluminium carbon composite cathode material

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Application publication date: 20180223