CN107732188A - A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application - Google Patents
A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application Download PDFInfo
- Publication number
- CN107732188A CN107732188A CN201710922721.1A CN201710922721A CN107732188A CN 107732188 A CN107732188 A CN 107732188A CN 201710922721 A CN201710922721 A CN 201710922721A CN 107732188 A CN107732188 A CN 107732188A
- Authority
- CN
- China
- Prior art keywords
- copper
- silicon
- aluminium
- parts
- nanoalloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
Abstract
A kind of heat treatment method of copper aluminium silicon Nanoalloy material of the present invention 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 one kind using heat treatment method processing copper alusil alloy nano material and its application, the technical scheme used for:Described heat treatment method is carried out after being dried in vacuo after dispensing, melting, powder processed, separation and screening step, dried copper aluminium silicon alloy nano-powder is heat-treated, heat treatment temperature is 250~500 DEG C, and the time is 48~90h;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
Technical field
A kind of heat treatment method of copper-aluminium-silicon Nanoalloy material of the present invention and its application, belong to lithium cell cathode material
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 is using heat treatment method processing copper-aluminium-silicon alloys nanometer material
Material and its application.
In order to solve the above technical problems, the technical solution adopted in the present invention is:Described heat treatment method be dispensing,
Carried out after being dried in vacuo after melting, powder processed, separation and screening step, by dried copper-aluminium-silicon alloy nano-powder
It is heat-treated, heat treatment temperature is 250~500 DEG C, and the time is 48~90h;The composition of described copper-aluminium-silicon Nanoalloy
For 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.
Further, described heat treatment method also includes:First being vacuumized under Equipment for Heating Processing cold conditions, vacuum≤ 0.1Pa, then from protective gas is persistently led to, after pressure is more than or equal to atmospheric pressure, reheat, in heating process so that heating
Room keeps malleation;Described protective gas is inert gas, or is nitrogen.
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 heat treatment method using copper-aluminium-silicon Nanoalloy material is preparing answering for lithium ion battery negative material
With.
A kind of application using the heat treatment method of copper-aluminium-silicon Nanoalloy material on lithium ion battery is prepared.
The present invention has the advantages that compared with prior art:
Heat treatment method of the present invention be after dispensing, melting, powder processed, separation and screening step be dried in vacuo it is laggard
Capable, dried copper-aluminium-silicon alloy nano-powder is heat-treated, heat treatment temperature is 250~500 DEG C, the time 48
~90h;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, described heat treatment method also includes:It is first that Equipment for Heating Processing is cold
Vacuumized under state, vacuum≤0.1Pa, then from protective gas is persistently led to, after pressure is more than or equal to atmospheric pressure, reheat,
In heating process so that heating chamber keeps malleation;Described protective gas is inert gas, or is nitrogen.Described receives
Rice alloy material integrally includes:Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structure structures in hole, it is obtained after being atomized
More than 90% is can reach to particle diameter≤80 μm.Alloy nano-material internal stress after being heat-treated substantially eliminates, product items
Energy 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 heat treatment method of the present invention is carried out after being dried after dispensing, melting, powder processed, separation and screening step
, dried copper-aluminium-silicon alloy nano-powder is heat-treated, using electric and magnetic oscillation timeliness instrument, electric and magnetic oscillation frequency
3000~5000Hz, time of vibration 100-150 hours;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;Described alloy nano-material is whole
Body includes:Stomata, shrinkage cavity and porosity, dislocation, room and more defect(ive) structure structures in hole, it obtains particle diameter≤80 μm after being atomized
It can reach more than 90%.Alloy nano-material internal stress after being heat-treated substantially eliminates, product properties uniformity compared with
It is good.
Embodiment 1:
(1)The dispensing of Cu-Al-Si alloys,
Fine copper is cut into φ 50mm × 100mm bars, adds drying to pre-process with pickling using preceding, drying temperature is controlled 110 ± 5
℃;Fine aluminium is cut into the small aluminium sheets of 50mm × 50mm × 30mm, adds drying to pre-process with pickling using preceding, drying temperature control exists
200±5℃;The lumpiness of metallic silicon is controlled in 5~30mm, is removed surface impurity using preceding pickling, is then dried, drying temperature
Degree control is at 180 ± 5 DEG C.Dispensing gross weight 20Kg, wherein by weight:22~27.5 parts of silicon, 60~70 parts of copper, aluminium
0.5~10 part, 0~5 part of impurity, impurity includes:Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon etc., first plus part silicon, then by copper and aluminium
Add, 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:Open
Open the middle packet system of atomising device, 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 be according to actual process flexible modulation.
(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 drying oven, pump is opened, stove negative pressure is reached 0.1Mpa, drying oven starts to rotate with 60r/min, opens heating system and carries out
Heating, makes heating-up temperature reach 180 DEG C.Drying time is 6h, stops heating, continues to rotate, and 3h is cooled down, 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:
Described heat treatment method is carried out after being dried in vacuo after dispensing, melting, powder processed, separation and screening step,
Dried copper-aluminium-silicon alloy nano-powder is heat-treated, heat treatment temperature be 250~500 DEG C, the time be 48~
90h;Described heat treatment method also includes:First being vacuumized under Equipment for Heating Processing cold conditions, vacuum≤0.1Pa, then from holding
Continuous logical protective gas, after pressure is more than or equal to atmospheric pressure, is reheated, in heating process so that heating chamber keeps malleation;It is described
Protective gas or be inert gas, or be nitrogen.
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, subsequently heat-treated, make
Obtain Nanoalloy internal stress to substantially eliminate, material property uniformity is good;Lithium ion battery negative material and lithium ion battery are made,
Its tap density approaches with graphite cathode material;Specific surface area only has half of graphite cathode material or so;Gram volume is graphite
1.5~2.8 times of negative material;First all efficiency of copper alusil alloy powder of the present invention and graphite it is close.Graphite cathode material
Cycle efficieny with circulation conservation rate about 98%, the cycle efficieny of copper of the present invention-aluminium-silicon alloys powder and circulation conservation rate
It is close with graphite.
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, other 0~5 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1550 ± 50 DEG C, other steps
Substantially similar to embodiment 1 with method, shown in Fig. 6-10, the performance of its final products of the present embodiment with embodiment 1 is also basic
It is 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, other 0~5 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1650 ± 50 DEG C, other steps and side
Method is substantially similar to embodiment 1, shown in Figure 11-20, the performances of its final products of the present embodiment with embodiment 1 also basic phase
Together.
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, other 0~3 part of impurity, the tapping temperatures of molten state copper-aluminium-silicon alloys are 1360 ± 50 DEG C, other steps and
Method is substantially similar to embodiment 1, shown in Figure 21-25, the performances of its final products of the present embodiment with embodiment 1 also basic phase
Together.
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, other 0~3 part of impurity, the tapping temperatures of molten state copper-aluminium-silicon alloys are 1600 ± 50 DEG C, other steps and
Method is substantially similar to embodiment 1, shown in Figure 26-30, the performances of its final products of the present embodiment with embodiment 1 also basic phase
Together.
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, other 0~5 part of impurity, the tapping temperature of molten state copper-aluminium-silicon alloys is 1350 ± 50 DEG C, other steps
Substantially similar to embodiment 1 with method, shown in Figure 31-35, the performance of its final products of the present embodiment with embodiment 1 is also basic
It is 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)
- A kind of 1. heat treatment method of copper-aluminium-silicon Nanoalloy material, it is characterised in that:Described heat treatment method be with Carried out after being dried in vacuo after material, melting, powder processed, separation and screening step, by dried copper-aluminium-silicon Nanoalloy Powder is heat-treated, and heat treatment temperature is 250~500 DEG C, and the time is 48~90h;Described copper-aluminium-silicon Nanoalloy Composition 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.
- 2. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 1, it is characterised in that described Heat treatment method also include:First being vacuumized under Equipment for Heating Processing cold conditions, vacuum≤0.1Pa, then from persistently logical protection Property gas, after pressure is more than or equal to atmospheric pressure, reheat, in heating process so that heating chamber keeps malleation;Described protectiveness Gas is inert gas, or is nitrogen.
- 3. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:22~27.5 parts of silicon, 60~70 parts of copper, 0.5~10 part of aluminium are miscellaneous 0~5 part of matter。
- 4. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:27.5~32 parts of silicon, 58~63 parts of copper, 1~11 part of aluminium, impurity 0~5 part.
- 5. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:32~39 parts of silicon, 54~59 parts of copper, 1~8 part of aluminium, impurity 0~ 5 parts.
- 6. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:37~42 parts of silicon, 55~62 parts of copper, 4~15 parts of aluminium, impurity 0 ~3 parts.
- 7. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:42~46 parts of silicon, 50~58 parts of copper, 5~15 parts of aluminium, impurity 0 ~3 parts.
- 8. the heat treatment method of a kind of copper-aluminium-silicon Nanoalloy material according to claim 2, it is characterised in that described Copper-aluminium-silicon Nanoalloy composition for by weight:50~70 parts of silicon, 20~40 parts of copper, 0.5~10 part of aluminium, impurity 0~5 part.
- 9. prepared by a kind of heat treatment method of copper-aluminium-silicon Nanoalloy material using described in claim 1-8 any one The application of lithium ion battery negative material.
- 10. a kind of heat treatment method of copper-aluminium-silicon Nanoalloy material using described in claim 1-8 any one is being made Application on standby lithium ion battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710922721.1A CN107732188A (en) | 2017-09-30 | 2017-09-30 | A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710922721.1A CN107732188A (en) | 2017-09-30 | 2017-09-30 | A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107732188A true CN107732188A (en) | 2018-02-23 |
Family
ID=61209332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710922721.1A Pending CN107732188A (en) | 2017-09-30 | 2017-09-30 | A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107732188A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101233633A (en) * | 2005-07-25 | 2008-07-30 | 3M创新有限公司 | Alloy compositions for lithium ion batteries |
CN102569757A (en) * | 2011-12-23 | 2012-07-11 | 西安交通大学 | Process for preparing materials of negative electrodes of copper-silicon-aluminum nano-porous lithium-ion batteries |
-
2017
- 2017-09-30 CN CN201710922721.1A patent/CN107732188A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101233633A (en) * | 2005-07-25 | 2008-07-30 | 3M创新有限公司 | Alloy compositions for lithium ion batteries |
CN102569757A (en) * | 2011-12-23 | 2012-07-11 | 西安交通大学 | Process for preparing materials of negative electrodes of copper-silicon-aluminum nano-porous lithium-ion batteries |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110061191B (en) | Three-dimensional metal lithium cathode and preparation method and application thereof | |
CN100457954C (en) | High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof | |
WO2002021616A1 (en) | Negative electrode for lithium secondary cell and method for producing the same | |
CN109509877A (en) | Carbon coating porous metal coating collector, preparation method and lithium battery | |
CN106611847A (en) | Preparation method of titanium-doped nano tungsten oxide negative electrode material | |
CN108075105A (en) | A kind of preparation method of lithium ion battery silicon-based anode | |
CN109524656A (en) | A kind of preparation method of lithium ion battery titanium oxide/silica negative electrode material | |
CN111187948A (en) | Phase-component-controllable lithium-aluminum alloy negative electrode material, and preparation method and application thereof | |
CN110224122A (en) | The preparation method of prelithiation alloy with porous structure | |
CN107732196A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN103924130B (en) | A kind of aluminium alloy/316L stainless steel coating matrix material and preparation method thereof | |
CN107790712A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN107123811B (en) | Dual-scale porous copper-aluminum-manganese shape memory alloy composite material and preparation method and application thereof | |
CN106702191B (en) | A kind of ferrotianium yttrium base hydrogen storage material and intermediate alloy and preparation method | |
CN103921493B (en) | A kind of alloy matrix aluminum/NiAl coating composite material and preparation method thereof | |
CN103658641A (en) | Magnesium base composite hydrogen storage material and preparation method thereof | |
CN107706386A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN107732197A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN107779661A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN107732191A (en) | A kind of copper alusil alloy material and its application | |
CN107723506A (en) | A kind of copper alusil alloy nanometer anode material of lithium battery and preparation method thereof | |
CN107732190A (en) | A kind of method and its application that copper alusil alloy powder is prepared using water atomization | |
CN107732188A (en) | A kind of heat treatment method of copper aluminium silicon Nanoalloy material and its application | |
CN107760921A (en) | A kind of vibration stress relief treatment method and its application of copper aluminium silicon Nanoalloy material | |
CN107732198A (en) | A kind of copper aluminium silicon Nanoalloy material covers carbon processing method and its application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180223 |