CN106784766B - A kind of preparation method and application of the porous negative electrode material for lithium ion battery - Google Patents
A kind of preparation method and application of the porous negative electrode material for lithium ion battery Download PDFInfo
- Publication number
- CN106784766B CN106784766B CN201611164431.7A CN201611164431A CN106784766B CN 106784766 B CN106784766 B CN 106784766B CN 201611164431 A CN201611164431 A CN 201611164431A CN 106784766 B CN106784766 B CN 106784766B
- Authority
- CN
- China
- Prior art keywords
- alloy
- negative electrode
- germanium
- electrode material
- preparation
- 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.)
- Expired - Fee Related
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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 preparation method of the porous negative electrode material for lithium ion battery, preparation step is as follows: preparing Ge-Si-Al alloy pig first, band is got rid of into again, as de- alloy presoma, it finally is made into bimodal nanoporous germanium-silicon alloy using de- alloy technology, as the porous negative electrode material of lithium ion battery.The application of the porous negative electrode material of prepared lithium ion battery, for assembling half-cell.The invention has the advantages that the characteristics of this method is dissolved mutually using germanium and silicon, bimodal nanoporous germanium-silicon alloy is prepared in conjunction with de- alloy approach, the nano-porous structure porosity of the material is higher, pitch of holes is suitable, can buffers active substance charging when volume expansion, further enhance the cycle life of negative electrode material；Have the characteristics that cost of material is low, preparation process is simple, process cycle is short, this material shows higher specific capacity and cyclical stability as the negative electrode material of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of for the porous of lithium ion battery
The preparation method and application of negative electrode material.
Background technique
Lithium ion battery is since its specific energy is big, operating voltage is high, stable circulation is good, can be quickly charged and discharged and without environment dirt
The advantages that dye, has obtained more concern.And the performance of lithium ion battery is largely determined by the electrode material of lithium ion battery
Material.Ion cathode material lithium can be divided into three classes according to its mechanism, lithium ion embedded category cathode, shift to new management mechanisms cathode and alloy machine
Cathode processed.Wherein, the theoretical capacity of the embedded cathode of the tradition such as graphite, lithium titanate only has 372mAh/g and 175mAh/g respectively.
With the development of lithium ion battery, the cathode such as conventional graphite and lithium carbonate can gradually be born by other with high capacity high stability
Pole material replaces.
Currently, as the germanium and silicon for being all IVA race element being all that good lithium ion is negative compared with graphite negative electrodes material
Pole material, and the capacity of this two is above graphite.In germanium and silicon alloy, the capacity (4200mAh/g) of silicon is higher than germanium
Capacity (1600mAh/g)；And germanium is lower than the forbidden bandwidth (1.12eV) of silicon due to its forbidden bandwidth (0.67eV), so germanium conducts
The ability of electronics is better than silicon.Therefore, research germanium-silicon alloy negative electrode material can be utilized respectively their advantage, both improve battery appearance
Amount improves conductivity again.However germanium silicium cathode material can have big volume expansion (about 400%) during the charging process, make
Active materials dusting falls off, to destroy the structure of material, reduce the embedding lithium ability of material, causes the stability of battery
And safety is unable to reach using standard, furthermore established SEI film holds in circulation volume expansion every time with during contraction
It easily ruptures, germanium-silicon alloy is made directly to generate new SEI film with electrolyte contacts.There is insulating property (properties) after being repeatedly circulated throughout
SEI film progressive additive, reduce the electro-chemical activity of material, cause capacitance loss.Therefore making for germanium silicium cathode material is improved
With service life (cyclical stability) and safety, it is necessary to which the volume expansion for reducing germanium-silicon alloy damages performance bring.
In the prior art, it is negative to disclose a kind of compound porous silicon of the carbon nanotube for lithium ion battery by CN106058256A
The preparation method of pole material.The invention mainly includes that thermal reduction prepares porous silicon, chemical vapour deposition technique carries out porous silicon
Carbon coating and composite carbon nanometer tube, acid processing removal iron catalyst.The invention is using works such as thermal reduction, chemical vapour deposition techniques
Skill keeps the material preparation process period long, low output；And the magnesium powder in experimentation is inflammable and explosive, there are security risks.
CN103985836A discloses a kind of method that germanium negative electrode material is prepared on nickel nanoneedle cone array.The invention is first Ni-based
Method on body using aqueous solution electro-deposition prepares the nickel nanoneedle cone array of certain altitude, then the environment hydrophobic in anaerobism
In, germanium negative electrode material is prepared on nickel nano needle arrays using the method for ionic liquid electrodeposition.The germanium particle of this method preparation
Size is larger, material porosity is not high, and preparation process is complicated, long preparation period, low output.(the Nano Energy such as S.Liu
2015,13:651-657) nanoporous germanium is prepared using de- alloying technology, by it as the cathode of high performance lithium ion battery
Material, compared to silicon, the capacity of germanium is lower, and Ge content is more (for 28.4at.%) in its presoma alloy use, cost compared with
It is high.
Summary of the invention
The purpose of the present invention is above-mentioned to solve the problems, such as, a kind of porous cathode material for lithium ion battery is provided
The characteristics of preparation method and application of material, this method is dissolved mutually using germanium and silicon, bimodal receive is prepared in conjunction with de- alloy approach
Meter Duo Kong germanium-silicon alloy, this material show higher specific capacity and cyclical stability as the negative electrode material of lithium ion battery.
Technical solution of the present invention:
A kind of preparation method of the porous negative electrode material for lithium ion battery, steps are as follows:
1) preparation of Ge-Si-Al alloy pig
It is the germanium block of 99.99wt%, silicon grain, aluminium block as raw material using purity, according to subject alloy ingredient
GexSixAl100-2xAtomic ratio stock up, wherein 8≤x≤11, when stock the standby amount of raw material respectively multiplied by a correction factor, with
Composition tolerances caused by scaling loss when cutting down alloy melting, the correction factor are respectively germanium 1.01, silicon 1.02, aluminium 1.05, are incited somebody to action
Load weighted raw material use arc melting method melting, and vacuum degree is evacuated to 9 × 10 after material shove charge-4Pa then passes to high-purity argon
Gas is first smelted into primary alloy ingot to -0.05MPa, by germanium and silicon, the independent melting ingot of aluminium, then by two groups of alloy pig meltings together,
Melt back 4 times to guarantee material refining uniformly, material with cold-crucible it is cooling after, obtain the Ge-Si-Al alloy refined
Ingot；
2) preparation of alloy presoma band is taken off
Above-mentioned alloy pig is put into quartz test tube, quartz ampoule nozzle diameter 1.1mm, quartz ampoule nozzle away from copper roll spacing from
2.1mm, induction heating melt alloy pig, are then quickly blown out the alloy of melting using argon gas, blow casting pressure and are
0.085MPa, quickly solidification forms alloy strip to the liquid alloy of melting on 3580 revs/min of revolving speed of copper roller, and band is made
Width be 2.3mm, with a thickness of 26 μm, as de- alloy presoma band；
3) preparation of bimodal nanoporous germanium-silicon alloy
De- alloy presoma band obtained above is placed in the hydrogen-oxygen that concentration is 2.0~2.3M, temperature is 63~67 DEG C
Change in sodium solution, freely takes off 400~420min of alloy, de- alloy product is pulled out cleaned repeatedly with deionized water after reaction
2 times, the remaining sodium hydroxide of sample surfaces is removed, de- alloy product is separated with centrifuge, is then being dried in vacuo product
Dried under 60 DEG C, -0.1Mpa in case, finally by bimodal nanoporous negative electrode material obtained be placed in vacuum degree be -0.1Mpa,
It is retained in the drying box that temperature is 25 DEG C spare.
A kind of application of the prepared porous negative electrode material for lithium ion battery, for assembling half-cell.
The preparation method of the above-mentioned porous negative electrode material for lithium ion battery, raw material used and equipment pass through public affairs
The approach known obtains, and operating procedure used is that those skilled in the art can grasp.
Beneficial effects of the present invention and substantive distinguishing features outstanding are:
The characteristics of present invention can be dissolved completely using germanium and silicon, prepares bimodal nanoporous germanium silicon in conjunction with de- alloy approach
Alloy material of cathode, this material combines the electronics conduction velocity of germanium with the embedding lithium ability height of silicon fastly, as lithium-ion electric
When the negative electrode material in pond, higher cyclical stability and specific capacitance, while the nano-porous structure porosity of the material are shown
It is higher, pitch of holes be suitable for, can buffers active substance charging when volume expansion, further enhance the circulation longevity of negative electrode material
Life.And have the characteristics that cost of material is low, preparation process is simple, process cycle is short, overcome prior art processes complexity, production
The disadvantages of period is long, energy consumption is high, material cost is high, low output.
Compared with prior art, marked improvement of the invention is as follows:
1. operation of the present invention condition is simple, require environmental condition low (normal temperature and pressure), requires low, preparation to working equipment
Period is short, yield is high, material preparation cost is low；
2. the porous anode material capacity of the present invention is high, potential plateau is low, is suitably applied negative electrode of lithium ion battery；
3. negative electrode material of the invention is bimodal nano-porous structure, enough spaces are provided for the expansion of material, are dropped
Generated stress when low material expansion reduces dusting and the degree to fall off, the cycle life for improving negative electrode material；
4. the advantages of the invention comprehensively utilizes silicon and germanium improves anode material capacity with pure germanium metal phase ratio, reduce
The cost of raw material, improves the electric conductivity of negative electrode material, and then increase the cyclical stability of material compared with pure silicon material.
Detailed description of the invention
Fig. 1 is the XRD spectrum of presoma alloy strip made from embodiment 1.
Fig. 2 is the XRD spectrum that alloy product is taken off made from embodiment 1.
Fig. 3 is the stereoscan photograph that alloy product is taken off made from embodiment 1.
Fig. 4 is the charging and discharging curve that 1 gained negative electrode material of embodiment is packaged into lithium ion battery.
Fig. 5 is the cycle performance and coulombic efficiency that 1 gained negative electrode material of embodiment is packaged into lithium ion battery.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment 1:
A kind of preparation method of the porous negative electrode material for lithium ion battery, steps are as follows:
1) preparation of Ge-Si-Al alloy pig
It is the germanium block of 99.99wt%, silicon grain, aluminium block as raw material using purity, according to subject alloy ingredient
Ge10Si10Al80Atomic ratio stock up, the standby amount of raw material is respectively multiplied by a correction factor when stock, when cutting down alloy melting
Scaling loss caused by composition tolerances.The scaling loss testing result obtained according to inventor's many experiments, correction factor are respectively germanium
1.01, load weighted raw material are used arc melting method melting by silicon 1.02, aluminium 1.05.After material shove charge vacuum degree be evacuated to 9 ×
10-4Pa then passes to high-purity argon gas and germanium and silicon is first smelted into primary alloy ingot, the independent melting ingot of aluminium to -0.05MPa, then incites somebody to action
Two groups of alloy pig meltings together, melt back 4 times to guarantee material refining uniformly, material with cold-crucible it is cooling after, refined
The Ge-Si-Al alloy pig made.
2) preparation of alloy presoma band is taken off
Above-mentioned alloy pig is put into quartz test tube, quartz ampoule nozzle diameter 1.1mm, quartz ampoule nozzle away from copper roll spacing from
2.1mm, induction heating melt alloy pig, are then quickly blown out the alloy of melting using argon gas, blow casting pressure and are
0.085MPa, quickly solidification forms alloy strip to the liquid alloy of melting on 3580 revs/min of revolving speed of copper roller, and band is made
Width be about 2.3mm, thickness is about 26 μm, as de- alloy persursor material.The XRD spectrum of presoma alloy strip is as schemed
Shown in 1, it is evident that the crystal peak of Ge, Si, Al, illustrate that material is Ge-Si-Al ternary alloy three-partalloy；
3) preparation of bimodal nanoporous germanium-silicon alloy
Presoma alloy strip obtained above is placed in the sodium hydroxide solution that concentration is 2.1M, temperature is 65 DEG C,
Alloy 410min is freely taken off, de- alloy product is pulled out cleaned repeatedly with deionized water 2 times after reaction, removes sample surfaces
Remaining sodium hydroxide is separated de- alloy product with centrifuge, then by product in a vacuum drying oven in 60 DEG C drying after,
Last nanoporous negative electrode material obtained is placed in the drying box that vacuum degree is -0.1Mpa, temperature is 25 DEG C retain it is spare.
Fig. 2 is the XRD diagram piece of de- alloy product, the peak of Ge, Si is only detected in map, and in part Ge solid solution and Si,
So that its diffraction maximum is broadened, but the peak of Al is not detected, Al element all filters out after illustrating de- alloy.Fig. 3 is de- alloy product
Stereoscan photograph.It is clear that the bimodal porous structure that material is made of hole/ligament of fine uniform in figure, one
About 0.5~1.6 μm of macropore diameter of grade, second level small aperture about 40~60nm.Last nanoporous negative electrode material obtained is set
It is -0.1MPa in vacuum degree, is retained in the drying box that temperature is 25 DEG C spare.
The assembling half-cell of the nanoporous germanium silicium cathode material made from the present embodiment is simultaneously tested for the property, and method is:
1) half-cell assembles: being that 7:2:1 weighs nanoporous germanium silicium cathode material prepared by the present invention respectively with mass ratio
Material, conductive black and binder sodium carboxymethylcellulose instill ultrapure water and paste are made, be uniformly applied to copper foil after being fully ground
On, cathode is used as after dry.Using 1M LiPF6As electrolyte, metal lithium sheet is used as to electrode, porous polypropylene
(Celgard) make diaphragm, carry out cell package.
2) battery performance test: 1) battery of assembling is tested for the property.Fig. 4 is the charge and discharge that battery is made in the present embodiment
Electrical testing curve, as seen from the figure, the electric discharge of battery first circle, charging capacitor amount are respectively 2776.2mAh/g and 2447.3mAh/g, library
Human relations efficiency is 88.15%.Fig. 5 is cycle performance of battery and coulombic efficiency test result, and as seen from the figure, battery illustrates good
Capacity performance, circulation is after 20 weeks, and charge/discharge capacity maintains 2200mAh/g or so, and coulombic efficiency is maintained at 99.6% or more.
Embodiment 2:
A kind of preparation method of the porous negative electrode material for lithium ion battery, steps are as follows:
1) Ge-Si-Al alloy pig prepare it is substantially the same manner as Example 1, the difference is that: subject alloy ingredient is
Ge8Si8Al84；
2) preparation for taking off alloy presoma band is identical with embodiment 1；
3) preparation of bimodal nanoporous germanium-silicon alloy
Presoma alloy strip obtained above is placed in the sodium hydroxide solution that concentration is 2.0M, temperature is 63 DEG C,
Alloy 400min is freely taken off, de- alloy product is pulled out cleaned repeatedly with deionized water 2 times after reaction, removes sample surfaces
Remaining sodium hydroxide is separated de- alloy product with centrifuge, then by product in a vacuum drying oven in 60 DEG C drying after,
It is -0.1MPa that last bimodal nanoporous negative electrode material obtained, which is placed in vacuum degree, is retained in the drying box that temperature is 25 DEG C
It is spare.The peak of Ge, Si are only detected in the XRD detection of de- alloy product, and Ge solid solution in part becomes its diffraction maximum with Si
Width, but the peak of Al is not detected, Al element all filters out after illustrating de- alloy.The de- alloy product is mainly by fine uniform
Hole/ligament composition bimodal porous structure, about 0.7~1.8 μm of level-one macropore diameter, second level small aperture about 50~80nm.
It is -0.1MPa that last nanoporous negative electrode material obtained, which is placed in vacuum degree, is retained in the drying box that temperature is 25 DEG C spare.
The assembling half-cell of the nanoporous germanium silicium cathode material made from the present embodiment is simultaneously tested for the property, and method is:
1) half-cell assembles: being that 7:2:1 weighs nanoporous germanium silicium cathode material prepared by the present invention respectively with mass ratio
Material, conductive black and binder sodium carboxymethylcellulose instill ultrapure water and paste are made, be uniformly applied to copper foil after being fully ground
On, cathode is used as after dry.Using 1M LiPF6As electrolyte, metal lithium sheet is used as to electrode, porous polypropylene
(Celgard) make diaphragm, carry out cell package.
2) battery performance test: 1) battery of assembling is tested for the property.The charge-discharge test curve of battery shows electricity
The electric discharge of pond first circle, charging capacitor amount are respectively 2753.3mAh/g and 2432.7mAh/g, coulombic efficiency 88.36%.Battery follows
Ring performance and coulombic efficiency test result show good capacity performance, and after 20 weeks, charge/discharge capacity is kept at circulation
2200mAh/g or so, coulombic efficiency are maintained at 99.7% or more.
Embodiment 3:
A kind of preparation method of the porous negative electrode material for lithium ion battery, steps are as follows:
1) Ge-Si-Al alloy pig prepare it is substantially the same manner as Example 1, the difference is that: subject alloy ingredient is
Ge11Si11Al78；
2) preparation for taking off alloy presoma band is identical with embodiment 1；
3) preparation of bimodal nanoporous germanium-silicon alloy
Presoma alloy strip obtained above is placed in the sodium hydroxide solution that concentration is 2.3M, temperature is 67 DEG C,
Alloy 420min is freely taken off, de- alloy product is pulled out cleaned repeatedly with deionized water 2 times after reaction, removes sample surfaces
Remaining sodium hydroxide is separated de- alloy product with centrifuge, then by product in a vacuum drying oven in 60 DEG C drying after,
It is -0.1MPa that last nanoporous negative electrode material obtained, which is placed in vacuum degree, is retained in the drying box that temperature is 25 DEG C spare.
The peak of Ge, Si are only detected in the XRD detection of de- alloy product, and Ge solid solution in part makes its diffraction maximum broaden, but not with Si
The peak for detecting Al, Al element all filters out after illustrating de- alloy.The de- alloy product is mainly by the hole of fine uniform/tough
Bimodal porous structure with composition, about 0.4~1.5 μm of level-one macropore diameter, second level small aperture about 30~60nm.It will finally make
It is -0.1MPa that the nanoporous negative electrode material obtained, which is placed in vacuum degree, is retained in the drying box that temperature is 25 DEG C spare.
The assembling half-cell of the nanoporous germanium silicium cathode material made from the present embodiment is simultaneously tested for the property, and method is:
1) half-cell assembles: being that 7:2:1 weighs nanoporous germanium silicium cathode material prepared by the present invention respectively with mass ratio
Material, conductive black and binder sodium carboxymethylcellulose instill ultrapure water and paste are made, be uniformly applied to copper foil after being fully ground
On, cathode is used as after dry.Using 1M LiPF6As electrolyte, metal lithium sheet is used as to electrode, porous polypropylene
(Celgard) make diaphragm, carry out cell package.
2) battery performance test: 1) battery of assembling is tested for the property.The charge-discharge test curve of battery shows electricity
The electric discharge of pond first circle, charging capacitor amount are respectively 2755.8mAh/g and 2436.9mAh/g, coulombic efficiency 88.43%.Battery follows
Ring performance and coulombic efficiency test result show good capacity performance, and after 20 weeks, charge/discharge capacity is kept at circulation
2200mAh/g or so, coulombic efficiency are maintained at 99.6% or more.
Comparative example 1:
By Ge5Si5Al90(atomic ratio) alloy is prepared into band, and other conditions are with embodiment 1, as the result is shown: very few
After germanium, element silicon make de- alloy treatment, continuous ligament structure can not be formed, obtains the granular material of germanium and silicon mixing, not
The negative electrode material of nano-porous structure is obtained, on the one hand granular germanium silicium cathode material drops material electronics transfer ability significantly
It is low, serious volume expansion can be led to the problem of when on the other hand charging, makes the reduction of circulating battery stability.Therefore the material is uncomfortable
Preferably it is used as high performance lithium ionic cell cathode material.
Comparative example 2:
By Ge15Si15Al70(atomic ratio) alloy is prepared into band, and other conditions are with embodiment 1, as the result is shown: excessive
Germanium, element silicon keep de- alloy reaction insufficient, can not form the ligament structure of continuous effective, material ligament broadens, porosity drops
Low, it is even more impossible to obtain the negative electrode material of bimodal nano-porous structure, volume expansion when cannot charge for germanium silicium cathode material is mentioned
For sufficient space, make the reduction of circulating battery stability.Therefore the material is not suitable for as high performance lithium ionic cell cathode material
Material.
Comparative example 3:
By Ge10Si10Al80(atomic ratio) alloy is prepared into band, and band is placed in concentration is 2.5M, temperature is 60 DEG C
In sodium hydroxide solution, alloy 450min is freely taken off, it is more to be unable to get bimodal nanometer with embodiment 1 as the result is shown for other conditions
Porous materials, volume expansion when cannot charge for germanium silicium cathode material provide sufficient space, make the reduction of circulating battery stability.
Therefore the material is not suitable for as high performance lithium ionic cell cathode material.
Above embodiments and comparative example illustrate that lithium ion battery with the preparation method of porous negative electrode material is by continuous
The different ratio of alloy, strict control alloy preparation condition and de- alloying technology are attempted, is repeatedly practiced, finally developing has
The negative electrode material of bimodal nano-porous structure.
Raw material used in above-described embodiment and equipment pass through well known approach and obtain, and operating procedure used is this
What those skilled in the art can grasp.
Claims (2)
1. a kind of preparation method of the porous negative electrode material for lithium ion battery, it is characterised in that steps are as follows:
1) preparation of Ge-Si-Al alloy pig
It is the germanium block of 99.99wt%, silicon grain, aluminium block as raw material using purity, according to subject alloy ingredient GexSixAl100-2x's
Atomic ratio is stocked up, wherein 8≤x≤11, the standby amount of raw material is respectively multiplied by a correction factor when stock, when cutting down alloy melting
Scaling loss caused by composition tolerances, the correction factor is respectively germanium 1.01, silicon 1.02, aluminium 1.05, by load weighted raw material
Using arc melting method melting, vacuum degree is evacuated to 9 × 10 after material shove charge-4Pa then passes to high-purity argon gas extremely -0.05MPa, will
Germanium and silicon are first smelted into primary alloy ingot, the independent melting ingot of aluminium, then by two groups of alloy pig meltings together, melt back 4 times to protect
It demonstrate,proves material refining uniformly, after material is with cold-crucible cooling, obtains the Ge-Si-Al alloy pig refined；
2) preparation of alloy presoma band is taken off
Above-mentioned alloy pig is put into quartz test tube, quartz ampoule nozzle diameter 1.1mm, quartz ampoule nozzle away from copper roll spacing from 2.1mm,
Induction heating melts alloy pig, is then quickly blown out the alloy of melting using argon gas, and blowing casting pressure is 0.085MPa, melting
Liquid alloy on 3580 revs/min of revolving speed of copper roller quickly solidification form alloy strip, be made band width be
2.3mm, with a thickness of 26 μm, as de- alloy presoma band；
3) preparation of bimodal nanoporous germanium-silicon alloy
De- alloy presoma band obtained above is placed in the sodium hydroxide that concentration is 2.0~2.3M, temperature is 63~67 DEG C
In solution, 400~420min of alloy is freely taken off, de- alloy product is pulled out cleaned repeatedly with deionized water 2 times after reaction,
The remaining sodium hydroxide of sample surfaces is removed, is separated de- alloy product with centrifuge, then in a vacuum drying oven by product
It is dried under 60 DEG C, -0.1Mpa, it is -0.1Mpa, temperature that bimodal nanoporous negative electrode material obtained, which is finally placed in vacuum degree,
It is spare to be retained in 25 DEG C of drying boxes.
2. the application prepared by a kind of claim 1 for the porous negative electrode material of lithium ion battery, it is characterised in that: be used for
Assemble half-cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611164431.7A CN106784766B (en) | 2016-12-16 | 2016-12-16 | A kind of preparation method and application of the porous negative electrode material for lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611164431.7A CN106784766B (en) | 2016-12-16 | 2016-12-16 | A kind of preparation method and application of the porous negative electrode material for lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106784766A CN106784766A (en) | 2017-05-31 |
| CN106784766B true CN106784766B (en) | 2019-05-24 |
Family
ID=58891596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611164431.7A Expired - Fee Related CN106784766B (en) | 2016-12-16 | 2016-12-16 | A kind of preparation method and application of the porous negative electrode material for lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106784766B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706385B (en) * | 2017-09-28 | 2022-04-19 | 清华大学 | Superfine nanocrystalline germanium-based material, preparation method and application thereof |
| CN110224122B (en) * | 2019-06-11 | 2021-07-02 | 北京工业大学 | Preparation method of prelithiation alloy with porous structure |
| CN110380036B (en) * | 2019-07-24 | 2022-04-12 | 福州大学 | Alloy material composite carbon nanotube and preparation method and application thereof |
| CN112670490A (en) * | 2019-12-31 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Titanium and/or zirconium-doped silicon-based negative electrode material, preparation method and lithium ion battery |
| CN112768663B (en) * | 2021-01-26 | 2022-06-03 | 惠州锂威新能源科技有限公司 | Nano porous silicon/carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN114094071A (en) * | 2021-11-11 | 2022-02-25 | 惠州锂威新能源科技有限公司 | Silicon-based negative electrode material and preparation method thereof, negative plate and lithium ion battery |
| CN115367760A (en) * | 2022-08-17 | 2022-11-22 | 贵州安达科技能源股份有限公司 | Porous silicon material, preparation method and application thereof, carbon-silicon composite material, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103733393A (en) * | 2012-03-26 | 2014-04-16 | 古河电气工业株式会社 | Negative electrode material for lithium ion secondary batteries, method for producing same, negative electrode for lithium ion secondary batteries using same, and lithium ion secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2529410A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
-
2016
- 2016-12-16 CN CN201611164431.7A patent/CN106784766B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103733393A (en) * | 2012-03-26 | 2014-04-16 | 古河电气工业株式会社 | Negative electrode material for lithium ion secondary batteries, method for producing same, negative electrode for lithium ion secondary batteries using same, and lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106784766A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106784766B (en) | A kind of preparation method and application of the porous negative electrode material for lithium ion battery | |
| CN106784640B (en) | Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery negative electrode containing silicon-based composite negative electrode material | |
| CN108336342B (en) | Si/SiOx/C composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN108427077A (en) | A kind of experimental method for analysing lithium using reference electrode monitoring cathode | |
| CN102569757B (en) | Process for preparing materials of negative electrodes of copper-silicon-aluminum nano-porous lithium-ion batteries | |
| CN103165874A (en) | Porous silicon negative material of lithium ion battery and preparation method and application of material | |
| CN110289408A (en) | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon | |
| CN109273704A (en) | A kind of lithium anode and preparation method thereof with high-ratio surface protective layer | |
| CN102255077A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN109616639A (en) | A kind of hard carbon cladding expansion microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery | |
| WO2018113267A1 (en) | Negative electrode material for lithium ion battery and preparation method therefor | |
| CN102983308A (en) | Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof | |
| JP2003100284A (en) | Lithium secondary battery | |
| CN108199020B (en) | Carbon-coated silicon anode material with micro-nano hierarchical structure and preparation method and application thereof | |
| CN110931725B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| US9088048B2 (en) | Silicon whisker and carbon nanofiber composite anode | |
| CN106602001B (en) | A kind of preparation method and application of the porous negative electrode material of lithium ion battery | |
| CN112980436A (en) | Carbon quantum dot derived carbon nanosheet composite silicon dioxide cathode material and preparation method thereof | |
| CN106532025B (en) | A kind of preparation method and application of the porous negative electrode material of lithium ion battery | |
| US20180277888A1 (en) | Electrodes for metal ion batteries and related materials, batteries and methods | |
| CN105375012A (en) | Si-Sn composite material used for Li-ion battery anode and preparation method thereof | |
| CN202585619U (en) | Novel lithium ion battery cathode and lithium ion battery employing cathode | |
| CN106356533A (en) | Negative electrode pole piece material of cylindrical lithium ion battery and preparation method | |
| CN110739445B (en) | Preparation method of nitrogen-doped carbon/graphene/silicon self-supporting body composite electrode | |
| CN107572545A (en) | A kind of titanium boride for lithium-sulfur cell chemistry trapping polysulfide and preparation method and 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190524 Termination date: 20201216 |