CN107732191A - A kind of copper alusil alloy material and its application - Google Patents
A kind of copper alusil alloy material and its application Download PDFInfo
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- CN107732191A CN107732191A CN201710922948.6A CN201710922948A CN107732191A CN 107732191 A CN107732191 A CN 107732191A CN 201710922948 A CN201710922948 A CN 201710922948A CN 107732191 A CN107732191 A CN 107732191A
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Abstract
A kind of copper alusil alloy material of the present invention and its application, belong to technical field of alloy material, overcome the deficiencies in the prior art of the present invention, there is provided a kind of high-performance lithium battery copper alusil alloy negative material and its application, the technical solution adopted in the present invention are：A kind of copper alusil alloy material, consists of the following parts by weight：22~70 parts of silicon, 20~70 parts of copper, 0.5~15 part of aluminium, 0~5 part of impurity, the present invention can be widely applied to lithium ion battery negative material field.
Description
Technical field
A kind of copper-aluminium-silicon alloys material of the present invention and its application, belong to technical field of alloy material.
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
Overcome the deficiencies in the prior art of the present invention, there is provided a kind of high-performance lithium battery with copper-aluminium-silicon alloys negative material and
It is applied.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of copper-aluminium-silicon alloys material, by such as
Lower parts by weight composition：22~70 parts of silicon, 20~70 parts of copper, 0.5~15 part of aluminium, 0~5 part of impurity.
Further, described alloy material consists of the following parts by weight：22~27.5 parts of silicon, 60~70 parts of copper, aluminium 0.5~
10 parts, 0~5 part of impurity.
Further, described alloy material consists of the following parts by weight：27.5~32 parts of silicon, 58~63 parts of copper, aluminium 1~11
Part, 0~5 part of impurity.
Further, described alloy material consists of the following parts by weight：32~39 parts of silicon, 54~59 parts of copper, 1~8 part of aluminium,
0~5 part of impurity.
Further, described alloy material consists of the following parts by weight：37~42 parts of silicon, 55~62 parts of copper, aluminium 4~15
Part, 0~3 part of impurity.
Further, described alloy material consists of the following parts by weight：42~46 parts of silicon, 50~58 parts of copper, aluminium 5~15
Part, 0~3 part of impurity.
Further, described alloy material consists of the following parts by weight：50~70 parts of silicon, 20~40 parts of copper, aluminium 0.5~10
Part, 0~5 part of impurity.
Further, described impurity is：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, any number of mixing of carbon.
A kind of copper-application of the aluminium-silicon alloys material as lithium ion battery negative material.
The application for the lithium ion battery that a kind of copper-aluminium-silicon alloys material is made.
A kind of copper-aluminium-silicon alloys material of the present invention has the advantages that compared with prior art：
A kind of copper-aluminium-silicon alloys material, consists of the following parts by weight：22~70 parts of silicon, 20~70 parts of copper, 0.5~15 part of aluminium,
Impurity（Including：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）0~5 part.With reticulated microstructure, copper-rich phase is three-dimensional mesh knot
Structure, it is lamellar structure, for the thickness of unilateral Silicon-rich synusia in 280-320nm, aluminium is dissolved in copper-rich phase and formed al-si eutectic, institute
The more defect(ive) structure structures in the alloy nano-material stated generally stomata, shrinkage cavity shrinkage porosity, dislocation, hole etc..
A kind of copper-aluminium-silicon alloys material can be applied to the negative pole for preparing lithium ion battery and other energy storage devices.
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 is between 20~77%, usual silicon bronze use casting rolled plate, bar, so siliceous
High alloy is measured to be 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 water atomization.The microstructure knot of atomization gained powder
Structure is unique, and copper-rich phase is three-dimensional mesh-structured, when Si-rich phase solidifies, is attached to Tong Bi both sides forming core and growth, the life of Si-rich phase
Long pattern is determined by the structural form of copper wall, it will usually grows into irregular lamellar structure, the thickness of unilateral Silicon-rich synusia
Degree is in 300nm or so.Substantial amounts of contraction cavity, empty mesh and substantial amounts of shrink defects are left in copper-rich grid element center, it
Can volumetric expansion of the partial offset silicon in charge and discharge process, copper-rich stereoscopic grid is to control body of the silicon in charge and discharge process
The primary structure that product collapses, 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 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 4 makes Nanoalloy Fine Texture of Material SEM image.
Figure 17 is the microstructure SEM image that the embodiment of the present invention 4 makes negative pole level piece.
Figure 18 is first all charging and discharging curves that the embodiment of the present invention 4 makes lithium battery.
Figure 19 is the stable circulation charging and discharging curve that the embodiment of the present invention 4 makes lithium battery.
Figure 20 is the circulation gram volume and efficiency curve that the embodiment of the present invention 4 makes lithium battery.
Figure 21 is that the embodiment of the present invention 5 makes Nanoalloy Fine Texture of Material SEM image.
Figure 22 is the microstructure SEM image that the embodiment of the present invention 5 makes negative pole level piece.
Figure 23 is first all charging and discharging curves that the embodiment of the present invention 5 makes lithium battery.
Figure 24 is the stable circulation charging and discharging curve that the embodiment of the present invention 5 makes lithium battery.
Figure 25 is the circulation gram volume and efficiency curve that the embodiment of the present invention 5 makes lithium battery.
Figure 26 is that the embodiment of the present invention 6 makes Nanoalloy Fine Texture of Material SEM image.
Figure 27 is the microstructure SEM image that the embodiment of the present invention 6 makes negative pole level piece.
Figure 28 is first all charging and discharging curves that the embodiment of the present invention 6 makes lithium battery.
Figure 29 is the stable circulation charging and discharging curve that the embodiment of the present invention 6 makes lithium battery.
Figure 30 is the circulation gram volume and efficiency curve that the embodiment of the present invention 6 makes lithium battery.
Figure 31 is that the embodiment of the present invention 7 makes Nanoalloy Fine Texture of Material SEM image.
Figure 32 is the microstructure SEM image that the embodiment of the present invention 7 makes negative pole level piece.
Figure 33 is first all charging and discharging curves that the embodiment of the present invention 7 makes lithium battery.
Figure 34 is the stable circulation charging and discharging curve that the embodiment of the present invention 7 makes lithium battery.
Figure 35 is the circulation gram volume and efficiency curve that the embodiment of the present invention 7 makes lithium battery.
Embodiment
A kind of embodiment 1, copper-aluminium-silicon alloys material, consists of the following parts by weight：22~27.5 parts of silicon, copper 60~70
Part, 0.5~10 part of aluminium, 0~5 part of impurity.
The preparation method of the copper of the present embodiment-aluminium-silicon alloys material follows the steps below：
（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 22~27.5 parts of silicon, 60~70 parts of copper, aluminium 0.5
~10 parts, impurity（Including：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）0~5 part of configuration, first add part silicon, then copper and aluminium are added
Enter, 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 control is used as inertia at 1350 ± 50 DEG C, using argon gas or nitrogen
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
In sealing state；In addition, in order to improve production efficiency and reduce cost, logical protective gas can not be had to, overall process does not have to yet
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 water atomization pulverization of Cu-Al-Si alloys：
When the temperature of liquid metals reaches 1350 ± 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 12mm, water atomization 300-450Mpa of pressure, 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, 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 is opened, vacuum drying oven negative pressure of vacuum is reached -0.09Mpa, drying oven starts to revolve with 60r/min
Turn, open heating system and heated, heating-up temperature is reached 180 DEG C.Drying time is 6h, stops heating, continues to rotate, cold
But 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 often in an atmosphere
Temperature.
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：
Powder is mixed with 10% sucrose, adds a certain amount of water, is placed in after stirring in vacuum drying oven in 500~600 DEG C of guarantors
2~4h of temperature, cools to 80 DEG C with the furnace and comes out of the stove.The sucrose can also use edible oil, or be replaced for carbonaceous materials such as starch.
Table 2 is that the physical parameter of the copper-aluminium-silicon alloys 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 the present embodiment-aluminium-silicon alloys material, consists of the following parts by weight：27.5~32 parts of silicon, 58~63 parts of copper, aluminium 1
~11 parts, 0~5 part of impurity.And follow the steps below：
（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, dispensing are pressed：27.5~32 parts of silicon, 58~63 parts of copper,
1~11 part of aluminium, impurity（Including：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon）0~5 part configures, first plus part silicon, then by copper and
Aluminium adds, then excess silicon is added, and is eventually adding other materials, plus bell, in order to improve production efficiency and reduce cost,
Logical protective gas can not had to, overall process does not have to atmosphere protection and sealing burner hearth.Also inert gas can be first passed through into stove, is ventilated
Begun to warm up after 5min.
（2）The smelting of Cu-Al-Si alloys：
Fusing power is gradually increased, smelting time is controlled in 20~30min so that furnace charge has preferably flowing into molten state
Property, tapping temperature is controlled at 1550 ± 50 DEG C.
（3）The gas-atomized powder of Cu-Al-Si alloys：
Argon gas powder by atomization, when the temperature of liquid metals reaches 1550 DEG C, there is preferable mobility, aerosolization can be started
Journey.Before aerosolization process is started, following preparation need to be carried out：Middle packet system should be opened, reaches tundish temperature
1200℃.Tundish internal diameter of leting slip a remark selects φ 8mm.Aerosolization pressure 20Mpa.When above index meets to require, start in
Between wrap in pour into liquid metals, 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 is opened, vacuum drying oven negative pressure of vacuum is reached -0.09Mpa, drying oven starts to revolve with 60r/min
Turn, open heating system and heated, heating-up temperature is reached 180 DEG C.Drying time is 6h, stops heating, continues to rotate, cold
But 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 often in an atmosphere
Temperature.
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：
Powder is mixed with 10% starch from sweet potato, a certain amount of water is added, is placed in after stirring in vacuum drying oven 600~800
DEG C insulation 2~4h, cool to 80 DEG C with the furnace and come out of the stove.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 3 below：
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 preparation method of the present embodiment lithium ion battery negative material follows the steps below：
（1）The dispensing of Cu-Al-Si alloys：
Fine copper is cut into φ 50 × 100mm bars, adds vacuum drying to pre-process with pickling using preceding, drying temperature is controlled 110
±5℃；Fine aluminium is cut into the small aluminium sheets of 50 × 50 × 30mm, adds vacuum drying to pre-process with pickling using preceding, drying temperature control
At 200 ± 5 DEG C；The lumpiness of metallic silicon is controlled in 5~30mm, is removed surface impurity using preceding pickling, is then carried out vacuum drying,
Drying temperature is controlled at 180 ± 5 DEG C.Dispensing gross weight 20Kg, proportion scale：Silicon 32~39%, copper 54~59%, aluminium 2~11%,
Other elements（Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, carbon total amount≤5%）, first add part silicon, then copper and aluminium are added, then residue
Silicon is added, and is eventually adding other materials, and plus bell, inert gas is first passed through into stove, is begun to warm up after the 5min that ventilates.
（2）The smelting of Cu-Al-Si alloys：
Fusing power is gradually increased, smelting time control is in 20~30min, tapping temperature control in 1650 ± 10 DEG C, logical argon gas
Protection, from the slag making materials of Henan factory production.
（3）The ultrasonic gas-atomized powder of Cu-Al-Si alloys：
Compressed air powder by atomization, when the temperature of liquid metals reaches 1450 DEG C, aerosolization process can be started.Starting gas
Before atomization process, following preparation need to be carried out：Middle packet system should be opened, tundish temperature is reached 800 DEG C.Tundish
Internal diameter of leting slip a remark selects φ 10mm.The flow velocity of supersonic airstream reaches 2.5 Mach, and the pulse frequency of supersonic airstream reaches
100KHz, stream pressure 15Mpa.When above index meets to require, start to pour into liquid metals into tundish, carry out mist
Change powder processed.
（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 is opened, vacuum drying oven negative pressure of vacuum is reached -0.09Mpa, drying oven starts to revolve with 60r/min
Turn, open heating system and heated, heating-up temperature is reached 180 DEG C.Drying time is 6h, stops heating, continues to rotate, cold
But 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 often in an atmosphere
Temperature.
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：
Powder is mixed with 10% edible oil, is placed in after stirring in vacuum drying oven and is incubated 2~4h at 750 DEG C, cooled to the furnace
80 DEG C are come out of the stove.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 4 below：
Shown in Figure 11-15, the performance of its final products of the present embodiment with embodiment 1 is also essentially identical.
Embodiment 4
The present embodiment, proportion scale is by weight：Silicon 32~37%, copper 62~68%, aluminium 1~8%, other elements（Titanium, cobalt,
Nickel, manganese, iron, boron, phosphorus, carbon total amount≤3%）, the tapping temperature of molten state copper-aluminium-silicon alloys is 1650 ± 50 DEG C, other steps
It is substantially similar to embodiment 1-3 with method, shown in Figure 16-20, the performance of its final products of the present embodiment Yu embodiment 1-3
It is essentially identical.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 5 below：
Embodiment 5
The present embodiment, proportion scale is by weight：Silicon 37~42%, copper 55~62%, aluminium 1~8%, other elements（Titanium, cobalt,
Nickel, manganese, iron, boron, phosphorus, carbon total amount≤3%）, the tapping temperature of molten state copper-aluminium-silicon alloys is 1360 ± 50 DEG C, other steps
It is substantially similar to embodiment 1-3 with method, shown in Figure 21-25, the performance of its final products of the present embodiment Yu embodiment 1-3
It is essentially identical.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 6 below：
Embodiment 6
The present embodiment, proportion scale is by weight：Silicon 42~46%, copper 50~58%, aluminium 5~15%, other elements（Titanium, cobalt,
Nickel, manganese, iron, boron, phosphorus, carbon total amount≤3%）, the tapping temperature of molten state copper-aluminium-silicon alloys is 1600 ± 50 DEG C, other steps
It is substantially similar to embodiment 1-3 with method, shown in Figure 26-30, the performance of its final products of the present embodiment Yu embodiment 1-3
It is essentially identical.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 7 below：
Embodiment 7
The present embodiment, proportion scale is by weight：Silicon 50~70%, copper 20~40%, aluminium 0.5~10%, other elements（Titanium,
Cobalt, nickel, manganese, iron, boron, phosphorus, carbon total amount≤5%）, the tapping temperature of molten state copper-aluminium-silicon alloys is 1350 ± 50 DEG C, other steps
Rapid and method is substantially similar to embodiment 1-3, shown in Figure 31-35, the performance of its final products of the present embodiment Yu embodiment 1-3
Also it is essentially identical.
The physical parameter of the copper of the present embodiment-aluminium-silicon alloys material is as shown in table 8 below：
Above content is to combine the further description that specific preferred embodiment is done to the present invention, it is impossible to assert this hair
Bright embodiment is only limitted to this, for general technical staff of the technical field of the invention, is not departing from this
On the premise of invention, some simple deduction or replace can also be made, should all be considered as belonging to the power of the invention by being submitted
Sharp claim determines scope of patent protection.
Claims (10)
1. a kind of copper-aluminium-silicon alloys material, it is characterised in that described alloy material consists of the following parts by weight：Silicon 22~70
Part, 20~70 parts of copper, 0.5~15 part of aluminium, 0~5 part of impurity.
2. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：22~27.5 parts of silicon, 60~70 parts of copper, 0.5~10 part of aluminium, 0~5 part of impurity.
3. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：27.5~32 parts of silicon, 58~63 parts of copper, 1~11 part of aluminium, 0~5 part of impurity.
4. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：32~39 parts of silicon, 54~59 parts of copper, 1~8 part of aluminium, 0~5 part of impurity.
5. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：37~42 parts of silicon, 55~62 parts of copper, 4~15 parts of aluminium, 0~3 part of impurity.
6. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：42~46 parts of silicon, 50~58 parts of copper, 5~15 parts of aluminium, 0~3 part of impurity.
7. a kind of copper-aluminium-silicon alloys material according to claim 1, it is characterised in that described alloy material is by as follows
Parts by weight form：50~70 parts of silicon, 20~40 parts of copper, 0.5~10 part of aluminium, 0~5 part of impurity.
A kind of 8. copper-aluminium-silicon alloys material according to claim 1-7 any one, it is characterised in that described impurity
For：Titanium, cobalt, nickel, manganese, iron, boron, phosphorus, any number of mixing of carbon.
9. a kind of copper-aluminium-silicon alloys material as described in claim 1-7 any one is as lithium ion battery negative material
Using.
A kind of 10. application for the lithium ion battery that copper-aluminium-silicon alloys material as described in requiring 1-7 any one is made.
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| CN113122749A (en) * | 2019-12-31 | 2021-07-16 | 山西沃特海默新材料科技股份有限公司 | Carbon source reinforcing agent, carbon source reinforcing alloy and preparation method thereof |
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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 |
| 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 |
| 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 |
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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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| CN113122749A (en) * | 2019-12-31 | 2021-07-16 | 山西沃特海默新材料科技股份有限公司 | Carbon source reinforcing agent, carbon source reinforcing alloy and preparation method thereof |
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