CN107723506A - A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof - Google Patents

A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof Download PDF

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CN107723506A
CN107723506A CN201710922739.1A CN201710922739A CN107723506A CN 107723506 A CN107723506 A CN 107723506A CN 201710922739 A CN201710922739 A CN 201710922739A CN 107723506 A CN107723506 A CN 107723506A
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copper
aluminium
silicon
powder
parts
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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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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0848—Melting process before atomisation
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

A kind of copper alusil alloy nanometer anode material of lithium battery of the present invention and preparation method thereof, belong to lithium cell cathode material technical field, the present invention provides a kind of copper alusil alloy nanometer anode material of high-performance lithium battery and preparation method thereof, the technical scheme used for：A kind of copper alusil alloy nanometer anode material of lithium battery, is made up of following raw material：32~37 parts of silicon, 62~68 parts of copper, 4~15 parts of aluminium, 0~5 part of impurity；Described alloy nano-material integrally includes：Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structure structures in hole, particle diameter≤80 μm, present embodiments can apply to lithium cell cathode material technical field.

Description

The copper of a kind of lithium battery-aluminium-silicon alloys nanometer anode material and preparation method thereof
Technical field
A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material of the present invention and preparation method thereof, belongs to cathode of lithium battery Field of material technology.
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 exist by the use of silicon as negative material use when subject matter：Cycle life is short, first all efficiency Length of low and discharge and recharge time.Design of alloy of the present invention is unique with heterogeneous microstructure, the granularity of atomization gained alloy powder It is reasonably distributed, coating of lithium-ion battery demand, while the lithium battery superior performance that the present invention makes can be met, there is cycle life It is long, the characteristics of first all efficiency highs and short discharge and recharge time.
The content of the invention
A kind of overcome the deficiencies in the prior art of the present invention, there is provided copper of high-performance lithium battery-aluminium-silicon alloys nanometer negative pole material Material and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of copper-aluminium-silicon alloys of lithium battery Nanometer anode material, it is made up of following raw material：32~37 parts of silicon, 62~68 parts of copper, 4~15 parts of aluminium, 0~5 part of impurity；
Described alloy nano negative material integrally includes：Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structures in hole Structure, particle diameter≤80 μm.
Further, described impurity is：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, any number of mixing of carbon.
A kind of method for the copper-aluminium-silicon alloys nanometer anode material for preparing lithium battery, including：Batching step；Melting walks Suddenly；Milling step；Separation and screening step；Vacuum drying step, it is characterised in that：Described melting step includes：Sensing adds Heat, 20~30min of smelting time reach molten state, and tapping temperature is 1450 ± 50 DEG C.
Further, described water atomization pulverization is as follows：
The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
Second step, the liquid temperature of regulation copper-aluminium-silicon alloys is when reaching 1450 ± 50 DEG C so that furnace charge is into molten state；
Start to pour into liquid metals into tundish, adjust water atomization 300~450Mpa of pressure, carry out water atomization pulverization.
Further, described milling step is gas-atomized powder, and described gas-atomized powder is as follows：
The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
Second step, when the liquid temperature of regulation copper-aluminium-silicon alloys reaches 1450 ± 50 DEG C, start to pour into liquid into tundish Metal, aerosolization 10~50Mpa of pressure is adjusted, carry out gas-atomized powder；
Source of the gas is pure air, or is argon gas, or is nitrogen.
Further, described milling step is ultrasonic gas-atomized powder, and described ultrasonic gas-atomized powder is as follows:
The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
Second step, when the liquid temperature of regulation copper-aluminium-silicon alloys reaches 1450 ± 50 DEG C, start to pour into liquid into tundish Metal, the flow velocity for adjusting supersonic airstream are 2~2.5 Mach, and the pulse frequency of supersonic airstream is 80~100KHz, air-flow pressure Power is 10~50Mpa, carries out gas-atomized powder,
Source of the gas is pure air, or is argon gas, or is nitrogen.
Further, it is described separation and screening step after be dried in vacuo after, in addition to when eliminate stress rear place Manage step.
Further, described post-processing step is to cover carbon processing method：By dried copper-aluminium-silicon alloys powder, contain Carbonizable substance, water are the ratio between by weight=80-100:1-2:8-11, be placed in after stirring in vacuum heat treatment furnace 600~ 800 DEG C of 2~4h of insulation cover carbon processing, cool to 80 DEG C with the furnace and come out of the stove, the carbonaceous material or be edible oil, or are shallow lake Powder, or be sucrose.
Further, described post-processing step is electric and magnetic oscillation aging process, electric and magnetic oscillation 3000~5000Hz of frequency, Time of vibration 24-150 hours.
Further, described post-processing step for heat treatment, heat treatment temperature be 250~500 DEG C, the time be 48~ 90h.The present invention has the advantages that compared with prior art：
A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material of the present invention, is made up of following raw material：Silicon 32~37 Part, 62~68 parts of copper, 4~15 parts of aluminium, 0~5 part of impurity；Described alloy nano-material integrally includes：Stomata, shrinkage cavity and porosity, Dislocation, room and more defect(ive) structure structures in hole, particle diameter≤80 μm.
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 28~35% 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 with circulation conservation rate about 98%, copper alusil alloy powder of the present invention Cycle efficieny and circulation conservation rate and graphite it is close.
Brief description of the drawings
Fig. 1 is the microstructure SEM image of the embodiment of the present invention 1.
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.
Embodiment
A kind of embodiment 1, copper-aluminium-silicon alloys nanometer anode material of lithium battery, silicon 32 is formed by following raw material ~37 parts, 62~68 parts of copper, 4~15 parts of aluminium, 0~5 part of impurity, described alloy nano negative material integrally includes：Stomata, contracting Hole, shrinkage porosite, dislocation, more defect(ive) structure structures in room and hole, particle diameter≤80 μm.
The present embodiment follows the steps below preparation：
（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, by 35 parts of silicon, 65 parts of copper, 10 parts of aluminium, impurity（Bag Include：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）3 parts of configuration, first add part silicon, then copper and aluminium are added, then excess silicon is added Enter, 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 1450 ± 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：
Specified work( Rate (KW) Inlet wire electricity Press (V) Inlet wire electricity Flow (A) Supporting transformation Device (KVA) Direct current Flow (A) Direct current Press (V) Medium frequency electric Press (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 water atomization pulverization of Cu-Al-Si alloys：
When the temperature of liquid metals reaches 1450 ± 50 DEG C, and when alloy has preferable mobility, water atomization can be started Process.Before water atomization process is started, following preparation need to be carried out：Middle packet system should be opened, reaches tundish temperature To 600 DEG C.Tundish internal diameter of leting slip a remark selects φ 6-14mm, water atomization 300-450Mpa of pressure, and when above index, meet will When asking, start to pour into liquid metals into tundish, carry out powder by atomization.
（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.
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；Make lithium-ion electric Pond negative material and lithium ion battery, its tap density approach 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.
Embodiment 2：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 32 parts, 62 parts of copper, 4 parts of aluminium, 0.5 part of impurity；Its preparation method is as follows：
（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, 32 parts of silicon, 62 parts of copper, 4 parts of aluminium, impurity（Including： Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）0.5 part of configuration, first add part silicon, then copper and aluminium 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 in table 1, fusing power is gradually increased, smelting time is controlled in 20~40min so that furnace charge Into molten state, there is preferable mobility, tapping temperature is controlled at 1450 ± 50 DEG C；, can also for improving performance
Using argon gas or nitrogen as inert protective gas, need continuously to lead to protective gas in fusion process, except charging, When skimming and pouring into a mould, should try one's best makes burner hearth be in sealing state.
（3）The powder by atomization of Cu-Al-Si alloys：
When the temperature of liquid metals reaches 1450 ± 50 DEG C, and when alloy has preferable mobility, aerosolization can be started Process.Before aerosolization process is started, following preparation need to be carried out：Middle packet system should be opened, makes the tundish temperature be Room temperature.Tundish internal diameter of leting slip a remark selects φ 6-14mm, aerosolization pressure 10-50Mpa, source of the gas or be pure air, or is Argon gas, or be nitrogen, when above index meets to require, start to pour into liquid metals into tundish, carry out powder by atomization.
（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, is pressed using 5-8Mpa The compressed air of power, carries out press filtration separation of solid and liquid, and 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：
Ageing Treatment is carried out to powder from electric and magnetic oscillation aging process, vibration frequency changes in the range of 3000~5000Hz, Time of vibration needs 24-150h.
Embodiment 3：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 37 parts, 68 parts of copper, 15 parts of aluminium, 5 parts of impurity；Its preparation method is as follows：
（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, 37 parts of silicon, 68 parts of copper, 15 parts of aluminium, impurity（Including： Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）5 parts of configuration, first add part silicon, then copper and aluminium are added, then excess silicon is added, open Begin to heat.
（2）The smelting of Cu-Al-Si alloys：
According to the intermediate frequency furnace technical parameter in table 1, fusing power is gradually increased, smelting time is controlled in 20~40min so that stove Expect into molten state, there is preferable mobility, tapping temperature is controlled at 1450 ± 50 DEG C；, can also for improving performance Using argon gas or nitrogen as inert protective gas, need continuously to lead to protective gas in fusion process, except feeding, skimming During with cast, should try one's best makes burner hearth be in sealing state.
（3）The powder by atomization of Cu-Al-Si alloys：
When the temperature of liquid metals reaches 1450 ± 50 DEG C, and when alloy has preferable mobility, ultrasonic gas can be started Atomization process.Before ultrasonic gasification is started, following preparation need to be carried out：Middle packet system should be opened, makes tundish Temperature is 1200 DEG C.Tundish internal diameter of leting slip a remark selects φ 6-14m m, and the flow velocity for adjusting supersonic airstream is 2~2.5 horses Conspicuous, the pulse frequency of supersonic airstream is 80~100KHz, and stream pressure is 10~50Mpa, carry out gas-atomized powder, source of the gas or For pure air, or it is argon gas, or is nitrogen.When above index meets to require, start to pour into liquid metals into tundish, Carry out powder by atomization.
（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, is pressed using 5-8Mpa The compressed air of power, carries out press filtration separation of solid and liquid, and 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：
Above-mentioned powder is placed into heat-treatment furnace, heat treatment temperature is 250~500 DEG C, and the time is 48~90h.
It can also carry out vacuum heat in a vacuum furnace, vacuum heat treatment temperature is 250~500 DEG C, the time is 48~ 90h, vacuum≤0.02Pa.
Embodiment 4：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 33
Part, 63 parts of copper, 5 parts of aluminium, 3 parts of impurity；Preparation method is identical with embodiment 1-3.
Embodiment 5：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 34 parts, 65 parts of copper, 12 parts of aluminium, 3 parts of impurity；Preparation method is identical with embodiment 1-3.
Embodiment 6：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 35 parts, 67 parts of copper, 14 parts of aluminium, 4 parts of impurity；Preparation method is identical with embodiment 1-3.
Embodiment 7：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 36 parts, 68 parts of copper, 2 parts of aluminium, 3 parts of impurity；Preparation method is identical with embodiment 1-3.
Embodiment 8：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 37 parts, 67 parts of copper, 15 parts of aluminium, 5 parts of impurity；Preparation method is identical with embodiment 1-3.
Embodiment 9：A kind of copper of lithium battery-aluminium-silicon alloys nanometer anode material, is made up of following raw material：Silicon 35 parts, 66 parts of copper, 8 parts of aluminium, 2 parts of impurity；Preparation method is identical with embodiment 1-3.
Above example 1-9 performance and structure is essentially identical.
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 1. copper of lithium battery-aluminium-silicon alloys nanometer anode material, it is characterised in that：It is made up of following raw material：Silicon 32~37 parts, 62~68 parts of copper, 4~15 parts of aluminium, 0~5 part of impurity；
    Described alloy nano negative material integrally includes：Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structures in hole Structure, particle diameter≤80 μm.
  2. 2. the copper of a kind of lithium battery according to claim 1-aluminium-silicon alloys nanometer anode material, it is characterised in that described Impurity be：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, any number of mixing of carbon.
  3. 3. a kind of method for the copper-aluminium-silicon alloys nanometer anode material for preparing lithium battery as claimed in claim 1 or 2, bag Include：Batching step；Melting step；Milling step；Separation and screening step；Vacuum drying step, it is characterised in that：Described is molten Refining step includes：Sensing heating, 20~30min of smelting time reach molten state, and tapping temperature is 1450 ± 50 DEG C.
  4. 4. according to the method for claim 3, it is characterised in that：Milling step is water atomization pulverization, described water atomization system Powder is as follows：
    The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
    Second step, the liquid temperature of regulation copper-aluminium-silicon alloys is when reaching 1450 ± 50 DEG C so that furnace charge is into molten state；
    Start to pour into liquid metals into tundish, adjust water atomization 300~450Mpa of pressure, carry out water atomization pulverization.
  5. 5. according to the method for claim 3, it is characterised in that：Milling step is gas-atomized powder, described aerosolization system Powder is as follows：
    The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
    Second step, the liquid temperature of regulation copper-aluminium-silicon alloys reach 1450 ± 50 DEG C, start to pour into liquid gold into tundish Category, aerosolization 10~50Mpa of pressure is adjusted, carry out gas-atomized powder；Source of the gas is pure air, or is argon gas, or is nitrogen.
  6. 6. according to the method for claim 3, it is characterised in that：Milling step is ultrasonic gas-atomized powder, described ultrasound Gas-atomized powder is as follows:
    The first step, opens the middle packet system of atomising device, and tundish internal diameter of leting slip a remark selects 6~14mm of φ；
    Second step, when the liquid temperature of regulation copper-aluminium-silicon alloys reaches 1450 ± 50 DEG C, start to pour into liquid into tundish Metal, the flow velocity for adjusting supersonic airstream are 2~2.5 Mach, and the pulse frequency of supersonic airstream is 80~100KHz, air-flow pressure Power is 10~50Mpa, carries out gas-atomized powder；
    Source of the gas is pure air, or is argon gas, or is nitrogen.
  7. 7. according to the method described in claim 4-6 any one, it is characterised in that：Carried out after the separation and screening step After vacuum drying, in addition to eliminate the post-processing step of stress.
  8. 8. according to the method for claim 7, it is characterised in that described post-processing step is to cover carbon processing method：By drying Copper afterwards-aluminium-silicon alloys powder, carbonaceous material, water are the ratio between by weight=80-100:1-2:8-11, it is placed in after stirring 2~4h is incubated at 600~800 DEG C to carry out covering carbon processing, cool to 80 DEG C with the furnace and come out of the stove in vacuum heat treatment furnace, the carbon containing thing Matter is edible oil, or is starch, or is sucrose.
  9. 9. according to the method for claim 7, it is characterised in that described post-processing step is electric and magnetic oscillation aging process, electricity Magnetic vibration 3000~5000Hz of frequency, time of vibration 24-150 hours.
  10. 10. according to the method for claim 7, it is characterised in that described post-processing step is is heat-treated, heat treatment temperature For 250~500 DEG C, the time is 48~90h.
CN201710922739.1A 2017-09-30 2017-09-30 A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof Pending CN107723506A (en)

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CN114335490A (en) * 2021-01-27 2022-04-12 郑州轻工业大学 Preparation method of C @ Cu @ Si composite porous negative electrode material of lithium ion battery

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CN101339990A (en) * 2008-08-27 2009-01-07 安泰科技股份有限公司 Negative electrode of lithium ionic secondary battery and preparing method thereof
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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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
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Publication number Priority date Publication date Assignee Title
CN114335490A (en) * 2021-01-27 2022-04-12 郑州轻工业大学 Preparation method of C @ Cu @ Si composite porous negative electrode material of lithium ion battery
CN114335490B (en) * 2021-01-27 2023-12-01 郑州轻工业大学 Preparation method of C@Cu@Si composite porous anode material of lithium ion battery

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Application publication date: 20180223