CN206564288U - A kind of porous silicon copper-plating electrode for lithium ion battery - Google Patents
A kind of porous silicon copper-plating electrode for lithium ion battery Download PDFInfo
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- CN206564288U CN206564288U CN201720165695.8U CN201720165695U CN206564288U CN 206564288 U CN206564288 U CN 206564288U CN 201720165695 U CN201720165695 U CN 201720165695U CN 206564288 U CN206564288 U CN 206564288U
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- ion battery
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The utility model discloses a kind of porous silicon copper-plating electrode for lithium ion battery.The porous silicon copper-plating electrode is cylinder, is made up of the porous silicon grain of copper facing；The porous silicon grain of copper facing is made up of shell and inner core, and shell is copper particle, and with porous nanometer structure, inner core is porous silicon.The preparation method comprises the following steps：（1）The pretreatment of polycrystalline silica flour；（2）Deposit Ag nano particles；（3）The preparation of porous silicon；（4）The preparation of shell；（5）The formation of electrode.In the utility model porous silicon copper-plating electrode, copper particle with silicon is organic is closely combined together, increase contact area, effectively reduce contact resistance, substantially increase the electric conductivity of electrode；Copper particle substantially limits volumetric expansion of the silicon during lithiumation, it can effectively prevent silicon from coming off separation down to lithium ion battery failure from the surface of collector during battery cycle charge-discharge, so as to improve life-span and its cyclical stability of lithium ion battery.
Description
Technical field
The utility model is related to technical field of lithium ion, and in particular to a kind of porous silicon for lithium ion battery is plated
Copper electrode.
Background technology
Lithium ion battery belongs to the chargeable electrochmical power source of green high-capacity, with voltage is high, energy density is big, cycle performance
The outstanding advantages such as good, the small, memory-less effect of self discharge, in delivery vehicle, portable electric appts, communication back-up source, sky
Between the field such as technology, national defense industry be widely applied.At present, it is general to use in commercialized lithium-ion battery system
Graphite-like carbon is as negative material, but the theoretical capacity of graphite only has 372mAh/g, and high rate performance is not good, develops new
High-capacity cathode material turns into study hotspot.The theoretical specific capacity of silicon is up to 4200 mAh/g, than the ratio of graphite negative electrodes material
The high an order of magnitude of capacity, and its Li insertion extraction current potential is moderate, in the earth's crust rich reserves, valency low with electrolyte reactivity
Lattice are cheap, are the ideal choses of lithium ion battery negative material of new generation.But, during the alloying reaction of silicon and lithium, silicon
Material can produce violent volumetric expansion (>400%), be easily caused active material drastically efflorescence occurs in cyclic process so that
Come off from copper current collector, silicon makes electrical contact with copper to be weakened so that battery cycle life rapid attenuation.Simultaneously as the body of silicon materials
Product bulking effect so that silicon materials can not produce firm surface solid dielectric film in the electrolytic solution, electrode structure is destroyed,
The silicon face newly exposed can constantly form new electronic isolation（SEI）Film, causes efficiency for charge-discharge to reduce, and accelerates capacity to decline
Subtract.
Utility model content
Expanded for effective buffer volumes, improve the adhesion of silicon and collector, the rupture for reducing silicon grain comes off, strengthen lithium
Starting efficiency, cyclical stability and the high rate performance of battery, the utility model provide a kind of for the porous of lithium ion battery
Silicon copper-plating electrode.
The utility model also provides a kind of preparation method of porous silicon copper-plating electrode for lithium ion battery.
The utility model is achieved through the following technical solutions.
A kind of porous silicon copper-plating electrode for lithium ion battery, the porous silicon copper-plating electrode is cylinder；It is described many
Hole silicon copper-plating electrode is made up of the porous silicon grain of copper facing；The copper facing silicon grain is made up of shell and inner core；The shell is by copper
Particle is constituted, and is porous nanometer structure between copper particle；The inner core is porous silicon.
A kind of preparation method of described porous silicon copper-plating electrode for lithium ion battery, comprises the following steps：
（1）The pretreatment of polycrystalline silica flour：Polycrystalline silica flour is immersed in HCl solution, the removal of impurity is gone, then be sieved through with standard
Filter, is cleaned up, standby；
（2）Deposit Ag nano particles：The polycrystalline silica flour cleaned up is soaked in AgNO3In HF mixed solution,
Polycrystalline silicon powder surface deposits to form Ag nano particles, standard screen filtering, cleans up；
（3）The presentation of porous silicon：The polycrystalline silica flour that surface deposited into Ag nano particles is soaked in HF and H2O2Mixing it is rotten
Lose in liquid, using Ag as catalyst, accelerate the reaction of silicon near Ag particles, react to form taper on polycrystalline silicon powder particle surface
Hole, standard screen filtering, cleans up, obtains porous silicon；
（4）The preparation of shell：Obtained porous silicon is soaked in the plating solution of copper ions, magnetic agitation to solution is without gas
Bubble is produced, standard screen filtering, is cleaned up, vacuum drying, is obtained copper facing porous silicon；Using Ag as catalyst, copper ion is set to exist
Aggregation is reduced around Ag；
（5）The formation of electrode：By obtained copper facing porous silicon, uniformly paving in a mold, sinters under protective atmosphere, obtains institute
State the porous silicon copper-plating electrode for lithium ion battery.
Further, step（1）In, the particle diameter of the polycrystalline silica flour is 350 ~ 450 mesh.
Further, step（1）In, the mass concentration of the HCl solution is 9 ~ 11%.
Further, step（1）In, the time of the immersion is 25 ~ 35min.
Further, step（2）In, the AgNO3In HF mixed solution, AgNO3Concentration for 0.01 ~
0.03mol/L, HF concentration are 1 ~ 3wt%.
Further, step（2）In, the time of the deposition is 1 ~ 3min.
Further, step（3）In, the HF and H2O2Hybrid corrosion liquid in, HF concentration is 2.5 ~ 3mol/L,
H2O2Concentration be 0.5 ~ 1.5wt%.
Further, step（3）In, the temperature of the reaction is 20 ~ 30 DEG C, and the time of reaction is 1.5 ~ 2.5h.
Further, step（4）In, the plating solution of the copper ions is by NaKC4H4O6·4H2O、CuSO4·5H2O、
HCHO, NaOH and H2O is formulated, in plating solution, NaKC4H4O6Concentration be 0.04 ~ 0.05gmL-1, CuSO4Concentration be
0.01~0.02g·mL-1, HCHO concentration is 9 ~ 10mLL-1, NaOH concentration is 0.01 ~ 0.02 gmL-1。
Further, step（4）In, the rotating speed of the magnetic agitation is 450 ~ 500rmin-1。
Further, step（4）In, the vacuum drying is 5 ~ 6h of baking at 30 ~ 60 DEG C.
Further, step（1）~（4）In, the standard screen is 900 ~ 1100 the polished standard screens；Described clean up be
Cleaned with deionized water.
Further, step（5）In, the protective atmosphere is hydrogen.
Further, step（5）In, the temperature of the sintering is 800 ~ 900 DEG C, and the time of sintering is 1 ~ 2h.
Further, step（5）In, the mould has in the size identical cylinder with porous silicon copper-plating electrode
Chamber.
Compared with prior art, the utility model has the following advantages that and beneficial effect：
（1）In porous silicon copper-plating electrode of the present utility model for lithium ion battery, porous silicon is tightly wrapped by copper particle
Wrap up in, it is organic to be closely combined together, increase contact area, effectively reduce contact resistance, be conducive to silicon fully to be connect with copper
Touch, so as to improve electric conductivity；
（2）In porous silicon copper-plating electrode of the present utility model for lithium ion battery, the loose structure between copper particle
Limit and accommodate volumetric expansion of the silicon in charging, can effectively prevent silicon during battery cycle charge-discharge from collector
Surface comes off separation down to lithium ion battery failure, so as to improve life-span and its cyclical stability of lithium ion battery；
（3）Porous silicon copper-plating electrode of the present utility model for lithium ion battery, during the embedding lithium of silicon, copper particle
Between loose structure be conducive to the transport of lithium ion in electrolyte, so as to ensure the normal discharge and recharge of lithium ion battery.
Brief description of the drawings
Fig. 1 is the cross-sectional view of the porous silicon copper-plating electrode prepared in embodiment 1；
Fig. 2 is the sectional view of the porous silicon grain of copper facing in the porous silicon copper-plating electrode for preparing in embodiment 1；
Fig. 3 is assembling schematic diagram of the porous silicon copper-plating electrode for lithium ion half-cell in embodiment 2.
Embodiment
To further understand the utility model, the utility model is described further with reference to the accompanying drawings and examples,
It should be understood that, the claimed scope of the utility model is not limited to the scope of embodiment statement, claim
Other unrequited embodiments of wide parameter are equally effective.
Embodiment 1
A kind of preparation of porous silicon copper-plating electrode for lithium ion battery, comprises the following steps：
The preparation of inner core
（1）The cleaning of polycrystalline silica flour：30min is soaked to the 10g polycrystalline silica flour of 400 mesh with 10wt%HCl solution, except impurity elimination
Matter；Filtered, and cleaned up with deionized water with 1000 the polished standard screens；
（2）Deposit Ag nano particles：The polycrystalline silica flour cleaned up is inserted into AgNO3With HF mixed solution（Mixing is molten
In liquid, AgNO3Concentration be 0.02mol/L, HF concentration is 2wt%）In, Ag 2min are deposited, are formed on the surface of polysilicon
The Ag of nano particle；Filtered, and cleaned up with deionized water with 1000 the polished standard screens；
（3）The presentation of porous silicon：The polycrystalline silica flour that deposited Ag particles is inserted into HF and H2O2Hybrid corrosion liquid（Mixing
In corrosive liquid, HF concentration is 2.5mol/L, H2O2Concentration be 1wt%）In, at 25 DEG C, reaction time 2h；Use 1000 purposes
Standard screen is filtered, and is cleaned up with deionized water, obtains porous silicon.
The wearing of shell
（4）The porous silicon of preparation is inserted by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and H2O prepare and
Into copper ions plating solution（In plating solution, NaKC4H4O6·4H2O concentration is 0.05gmL-1, CuSO4·5H2O concentration is
0.02g·mL-1, HCHO concentration is 10mLL-1, NaOH concentration is 0.02 gmL-1, remaining is H2O）In, use magnetic force
Agitator is with 500rmin-1Rotating speed stir to solution bubble-free produce；Filtered with 900 the polished standard screens, and spend from
Sub- water is cleaned up, 60 DEG C of vacuum drying 6h, obtains copper facing porous silicon.
The shaping of electrode
The porous silicon grain of copper facing is equably layered on the mould with a diameter of 15mm, highly for 0.5mm cylindrical cavities
In and be compacted locking；The mould of locking is inserted in vacuum resistance furnace, is incubated in the environment of 800 DEG C, hydrogen are as protection gas
1h, obtains the porous silicon copper-plating electrode for lithium ion battery.
A kind of porous silicon copper-plating electrode and the section view of the porous silicon grain of copper facing therein for lithium ion battery prepared
Respectively as depicted in figs. 1 and 2, porous silicon copper-plating electrode is cylinder to figure, and porous silicon copper-plating electrode is by the porous silicon grain structure of copper facing
Into copper facing silicon grain is made up of shell 10 and inner core 9, and inner core 9 is porous silicon, and shell 10 is made up of copper particle, between copper particle
For porous nanometer structure.
Embodiment 2
Porous silicon copper-plating electrode prepared by embodiment 1 be used for lithium ion half-cell in, assembling schematic diagram as shown in Fig. 2
From top to bottom include upper battery case 1, shell fragment 2, pad 3, lithium piece 4, barrier film 5, electrolyte 6, lower battery case 7 and porous silicon plating successively
Copper electrode 8；
Porous silicon copper-plating electrode 8 is placed on lower battery case 7, the direct invasion porous silicon copper-plating electrode 8 of electrolyte 6, electrolyte 6
Full of the whole cavity being made up of porous silicon copper-plating electrode 8, lower battery case 7 and barrier film 5；
Lithium piece 4 is close on barrier film 5, and the upper surface of lithium piece 4 is sequentially placed pad 3 and shell fragment 2, pad 3 from the bottom to top
Play a part of adjusting pressure with shell fragment 2；Shell fragment 2 is in close contact to reduce contact resistance with upper battery case 1, it is ensured that inside battery
Good electric conductivity.
After the completion of the assembling of lithium ion half-cell, during electric discharge, lithium piece 4 starts de- lithium, and lithium ion enters electrolysis by barrier film 5
In liquid 6, then contacted by the nano grade pore between copper particle on porous silicon copper-plating electrode electrode 8 with porous silicon and occur embedding lithium
Process；At the same time, electronics is successively by pad 3, shell fragment 2 and upper battery case 7, due to lower battery case 7 and porous silicon copper facing electricity
Pole 8 is in close contact, thus electronics enter in the porous silicon in porous silicon copper-plating electrode 8 with lithium ion carry out charging neutrality, it is complete
Into the discharge process of lithium ion half-cell, and the charging process of lithium ion half-cell is just opposite.
Described lithium ion half-cell, due to parcel of the copper particle to porous silicon, is added to many in charge and discharge process
The binding force of hole silicon, can efficiently control the expansion of porous silicon；The close contact of copper particle and porous silicon, is greatly reduced simultaneously
Contact resistance, adds electric conductivity.Porous nanometer structure between copper particle is conducive to the lithium ion in electrolyte to lead to easily
Cross, so with silica flour occur embedding and removing process, so as to ensure that battery can carry out normal discharge and recharge.
Above-described embodiment of the present utility model is only intended to clearly illustrate the utility model example, and is not
Restriction to embodiment of the present utility model.For those of ordinary skill in the field, on the basis of described above
On can also make other changes in different forms.There is no necessity and possibility to exhaust all the enbodiments.
All any modifications, equivalent substitutions and improvements made within spirit of the present utility model and principle etc., should be included in this reality
Within new scope of the claims.
Claims (4)
1. a kind of porous silicon copper-plating electrode for lithium ion battery, it is characterised in that the porous silicon copper-plating electrode is by copper facing
Porous silicon grain is constituted；The copper facing silicon grain is made up of shell and inner core；The shell is made up of copper particle.
2. a kind of porous silicon copper-plating electrode for lithium ion battery according to claim 1, it is characterised in that described outer
It is porous nanometer structure between the copper particle of shell.
3. a kind of porous silicon copper-plating electrode for lithium ion battery according to claim 1, it is characterised in that in described
Core is porous silicon.
4. a kind of porous silicon copper-plating electrode for lithium ion battery according to any one of claim 1 ~ 3, its feature exists
In the porous silicon copper-plating electrode is cylinder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598423A (en) * | 2018-04-25 | 2018-09-28 | 华南理工大学 | A kind of silicon carbon material and preparation method thereof for negative electrode of lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598423A (en) * | 2018-04-25 | 2018-09-28 | 华南理工大学 | A kind of silicon carbon material and preparation method thereof for negative electrode of lithium ion battery |
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