CN103779546A - Hollow structure material as well as preparation method and use thereof - Google Patents

Hollow structure material as well as preparation method and use thereof Download PDF

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CN103779546A
CN103779546A CN201410025915.8A CN201410025915A CN103779546A CN 103779546 A CN103779546 A CN 103779546A CN 201410025915 A CN201410025915 A CN 201410025915A CN 103779546 A CN103779546 A CN 103779546A
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hollow structure
structure material
particle
silicon
layer
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周萨
刘祖琴
韩松
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Nanjing Peace Jim Press Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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

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Abstract

The invention discloses a hollow structure material. The hollow structure material comprises silicon particles and an amorphous carbon shell, wherein the silicon particles are arranged in the amorphous carbon shell. The hollow structure material has the advantages that a hollow part between a silicon kernel and the carbon shell can be used for volume expansion of silicon; direct contact between the silicon and an electrolyte solution is blocked by a carbon shell membrane of a surface layer, so that a steady solid-state electrolyte solution interface can be formed on the surface of the carbon shell; and amorphous carbon is high in electronic conductivity and high in ionic conductivity, so that lithium ions and electrons can be freely transported through the amorphous carbon. A carbon-coated hollow material is applied to an existing slurry coating method electrode preparation technology and lays a foundation for industrial application. The invention also discloses a preparation method of the hollow structure material. The preparation method does not relate to dangerous gas such as silicane or similar expensive instruments for chemical vapor deposition. The large-scale production manufacturing of the hollow structure material is easily realized. A production condition control requirement is not strict, so that the hollow structure material is high in repeatability.

Description

A kind of hollow structure material and its production and use
Technical field
The invention belongs to electrochemical energy storage technical field, be specifically related to a kind of hollow structure material and its production and use.
Background technology
Along with the continuous expansion of mobile electron industry and ev industry, the energy density that how to improve electrochemical energy storage device has become a technical barrier more and more in the urgent need to address.It requires the electrode material of energy storage device to possess high volume capacity and quality capacity simultaneously, stable chemical property, low cost and manufacture on a large scale ability.The existing electrode material with high-quality and volume capacity, such as silicon, germanium, tin, tin oxide etc., because its change in volume violent in charge and discharge process causes the cyclical stability of material very poor.In addition, the unsettled solid electrolyte interface that its surface forms, has further limited their practical application.
In order to improve the cyclical stability of silicon isoreactivity material in charge and discharge process, researcher has been attempted many new methods and technology.Three work related to this are below enumerated.
1, silicon top layer wraps
(1)?“Carbon-Coated?Si?as?a?Lithium-Ion?Battery?Anode?Material”?J.?Electrochem.?Soc.?2002,?149,?A1598-A1603
(2)?“Electrochemical?stability?of?silicon/carbon?composite?anode?for?lithium?ion?batteries”?Electrochimica?Acta,?2007,?52,?4878-4883
(3)?“Carbon-coated?silicon?as?anode?material?for?lithium?ion?batteries:?advantages?and?limitations”?Electrochimica?Acta,?2003,?48,?1579-1587
In these documents, carbon or metal are used to wrap the surface at silicon.These surfaces wrap the effect that can play to a certain extent the cyclical stability of stable silicon, but it is easy to because the volumetric expansion of silicon is broken, and causes silicon to contact with the direct of electrolyte, thereby form unsettled solid electrolyte interface.
2, silicon dioxide wraps nano-tube
“Stable?cycling?of?double-walled?silicon?nanotube?battery?anodes?through?solid–electrolyte?interphase?control”?Nature?Nano.?2012,?7,?310-315
This piece of article described using silicon dioxide and wrapped nano-tube as Anode of lithium cell.Outer field silicon dioxide not only contributes to form stable solid electrolyte interface, and has fettered the outside expansion of silicon.Meanwhile, the space in the middle of tubular structure can be used to alleviate the ill effect that the volumetric expansion of silicon brings, thereby obtains good cycle performance.But because the manufacture of this material need to be used silane and CVD system, difficulty and the cost produced are improved greatly.
3, nano silicon particles embeds carbon nano-tube
(1)?“Engineering?Empty?Space?between?Si?Nanoparticles?for?Lithium-Ion?Battery?Anodes”?Nano?Lett.?2012,?12,?904-909
(2)?“Electrospun?Core–Shell?Fibers?for?Robust?Silicon?Nanoparticle-Based?Lithium?Ion?Battery?Anodes”?Nano?Lett.?2012,?12,?802-807
In these work, nano level silicon grain is embedded in carbon nano-tube.Because certain space has been reserved in the volumetric expansion that the hollow space of carbon nano-tube is silicon, the cycle performance of whole electrode is stablized.But this material also has certain limitation in practical application.First, the distribution of nano silicon particles in carbon nano-tube is difficult to control, thereby reduced the synthetic consistency of material.Secondly, enter in nanotube and directly touch silicon in order to reduce electrolyte, this method requires carbon nano-tube to have certain length, thereby has introduced another technical barrier.
Therefore, need a kind of new active material to address the above problem.
Summary of the invention
The present invention is directed to the poor defect of the cyclical stability of active material in charge and discharge process in prior art, a kind of cyclical stability that can improve electrode is provided, keep a kind of hollow structure material of high-energy-density simultaneously.
For solving the problems of the technologies described above, the technical scheme that hollow structure material of the present invention adopts is:
A kind of hollow structure material, comprises silicon grain and unsetting carbon shell, and described silicon grain is arranged in described unsetting carbon shell.
Further, as the anode of lithium battery, described silicon grain is by Ge particle, Sn particle, SnO 2particle, Al particle, Sb particle, TiO 2the alloying pellet of particle or above-mentioned material replaces;
As the negative electrode of lithium battery, described silicon grain is by LiCoO 2particle, LiFePO 4particle, LiMnO 2particle, LiNiO 2particle, LiMn 2o 4particle, LiCoPO 4particle, LiNi xco ymn 1-x-yo 2particle, LiNi xco yal zo 2particle, LiFe 2(SO4) 3particle or FeF 3particle replaces;
Described shell is by Al 2o 3layer, TiO 2layer, CdS layer or Fe 2o 3layer replaces.
Further, the size of described silicon grain is 1nm-100um, and the voidage between described silicon grain and unsetting carbon shell is (0,500%) of described silicon grain volume, and the thickness of unsetting carbon shell is (0,100nm).
Beneficial effect: hollow structure material of the present invention has the following advantages: first, the hollow parts between silicon core and carbon shell can be used for the volumetric expansion of silicon.The unsetting carbon shell membrane on top layer has cut off silicon and has contacted with the direct of electrolyte, thereby can form on the surface of carbon shell stable solid-state electrolytic solution interface.Secondly,, because unsetting carbon has good electronics and ionic conductivity, lithium ion and electronics can transport freely by it.The coated hollow material of this unsetting carbon is applicable to existing slurry cladding process (slurry coating) electrode fabrication, for its industrial applications is laid a good foundation.
The invention also discloses a kind of preparation method of hollow structure material.
The preparation method of hollow structure material of the present invention, comprises the following steps:
1), take silicon grain as original material, with heating method realize the oxidation to silicon grain surface, make the surface of silicon grain be coated with layer of silicon dioxide, obtain intermediate product A;
2), intermediate product A is joined in the tromethamine cushioning liquid that contains dopamine, above-mentioned mixed solution is stirred, until silicon and silica particles wrap last layer dopamine polymer, dry, obtain intermediate product B;
3), intermediate product B is placed on and in heating furnace, carries out carbonization, under argon shield, be warming up to 250-550 degree Celsius, heating 1-3 hour, be warming up to 650-1000 degree Celsius, heating 1-5 hour, through above-mentioned heating process, the dopamine polymer of dopamine polymer silicon and silica particles is converted into unsetting carbon, obtains intermediate product C;
4), intermediate product C is placed in HF solution and is reacted,, until remove the silicon dioxide layer in intermediate product C, obtain hollow structure material.
Further, the diameter that removes the silicon grain of silicon dioxide layer in the described hollow structure material obtaining in step 4) is 1nm-100um, and the volume of described silicon dioxide layer is (0,500%) of removing the silicon grain volume of silicon dioxide layer, the thickness of unsetting carbon-coating is (0,100nm).
Further, in the heating process described in step 1), pass into steam.Can accelerate oxidation rate.
Further, in step 3), under argon shield, be warming up to 400 degrees Celsius, heat 2 hours, be warming up to 800 degrees Celsius, heat 2.5 hours.
Further, step 2) in the concentration of tromethamine cushioning liquid be (0.001M, 10M), the mass ratio of intermediate product A and dopamine is 0.05-50:1.
Beneficial effect: the preparation method of hollow structure material of the present invention does not relate to the expensive instrument of hazardous gas such as silane or similar chemical vapor deposition (CVD) and so on.Its large-scale manufacturing is easy to realize.Not strict for working condition control requirement, thus the repeatability that hollow structure material is good guaranteed.
The invention also discloses a kind of purposes of hollow structure material, the purposes of hollow structure material as above in the electrode cyclical stability that improves lithium battery, lithium ion battery, ultracapacitor or lithium-air battery.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of hollow structure material of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of the hollow structure material for preparing of embodiment 1;
Fig. 3 is the principle schematic of hollow structure material of the present invention;
Fig. 4 is the electrochemistry cycle performance comparison diagram of hollow structure material of the present invention and independent silicon grain.
Embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate the present invention, should understand these embodiment is only not used in and limits the scope of the invention for the present invention is described, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Hollow structure material of the present invention, comprises silicon grain and unsetting carbon shell, and silicon grain is arranged in unsetting carbon shell.Wherein, the size of silicon grain is 1nm-100um, and the voidage between silicon grain and unsetting carbon shell is (0,500%) of silicon grain volume, and the thickness of unsetting carbon shell is (0,100nm).
Hollow structure material of the present invention has the following advantages: first, the hollow parts between silicon core and carbon shell can be used for the volumetric expansion of silicon.The unsetting carbon shell membrane on top layer has cut off silicon and has contacted with the direct of electrolyte, thereby can form on the surface of carbon shell stable solid-state electrolytic solution interface.Secondly,, because unsetting carbon has good electronics and ionic conductivity, lithium ion and electronics can transport freely by it.The coated hollow material of this unsetting carbon is applicable to existing slurry cladding process (slurry coating) electrode fabrication, for its industrial applications is laid a good foundation.
embodiment 1
The preparation method of hollow structure material, comprises the following steps:
1), take silicon grain as original material, with heating method realize the oxidation to silicon grain surface.Silicon grain is placed in to tubular type revolving burner and is heated to 1050 degrees Celsius, in this process, steam is constantly passed into accelerate oxidation rate.Silicon grain surface forms the oxide layer (silicon dioxide layer) of even thickness after high-temperature heating, obtains intermediate product A.Wherein, the thickness of oxide layer is controlled by adjusting the high-temperature heating time.
2) the intermediate product A, step 1) being obtained joins in the tromethamine cushioning liquid (PH=8,0.1M) that contains dopamine.The mass ratio of product A, dopamine and tromethamine cushioning liquid is 3:1:60, above-mentioned mixed solution is stirred, through the stirring of 24 hours, product A surface wraps last layer dopamine polymer, collect and dry in 110 degrees Celsius of vacuum environments by vacuum filtration, obtain product B.
3), by step 2) product B that obtains is placed on and in tubular type revolving burner, carries out carbonization; under the protection of Ar gas; be warming up to 400 degrees Celsius; heat 2 hours; be warming up to 800 degrees Celsius, heat 2.5 hours, through above-mentioned heating process; the dopamine polymer on product B surface is converted into unsetting carbon-coating, obtains product C.Wherein, the time that is warming up to 400 degrees Celsius and 800 degrees Celsius is respectively 5 hours and 1.5 hours.
4), product C that step 3) is obtained is placed in 10% HF solution and reacts, until remove the silicon dioxide layer in indefinite form carbon silicon and silica dioxide granule, obtains the Si hollow structure material being wrapped by unsetting carbon C.
Synthetic required raw material silica flour, can adopt existing ripe technique to carry out volume production, and this hollow structure material synthetic do not relate to the expensive instrument of hazardous gas such as silane or similar CVD and so on.Its large-scale manufacturing is easy to realize.The hollow material that this carbon wraps is applicable to existing slurry cladding process (slurry coating) electrode fabrication, for its industrial applications is laid a good foundation.Not strict for working condition control requirement, thus the repeatability that hollow structure material is good guaranteed.Wherein, Fig. 2 is the scanning electron microscope (SEM) photograph of the hollow structure material for preparing of embodiment 1.
Refer to shown in Fig. 3 the operation principle of hollow structure material of the present invention: in the process of embedding lithium, lithium ion, through unsetting carbon-coating, reacts with silicon grain.Silicon grain generation volumetric expansion, is filled into the gap in the middle of itself and carbon.Meanwhile, form stable solid electrolyte interface on the surface of carbon.In de-lithium and embedding lithium process subsequently, the structure of material can be not destroyed, thereby can obtain stable chemical property.
Refer to shown in Fig. 4, Fig. 4 has compared the electrochemistry cycle performance of hollow structure material of the present invention and independent silicon grain.It shown in figure, is the de-lithium capacity of two kinds of systems.The test rate of the first circulation is C/20, and the second cycle charging speed is C/20, and discharge rate is C/2.Hollow structure material and independent silicon grain are mixed with graphite with same proportioning respectively and be prepared into electrode with the method for slurry cladding process (slurry coating).With LiCoO 2for anode, the LiPF6 (10%FEC take concentration as 1M; EC:DEC:DMC=1:1:1) be electrolyte, the full cycle performance of battery of bi-material as shown in Figure 4.For guaranteeing the reliability of result, every group of experiment all carried out three times and repeated.Although independent silicon grain and hollow structure material have similar capacity in first circulation, the cyclical stability having clear improvement as basic battery take hollow structure material.Take the 3rd capacity circulating as 100%, to the 300th circulation, the capability retention of hollow structure material system is 86.7%.And for independent silicon grain system, capacity attenuation 23.0%.This organizes result and proves compared to independent silicon grain, and the cyclical stability of electrode, the high-energy-density that simultaneously keeps silicon to provide can be provided hollow structure material of the present invention greatly.
embodiment 2
The preparation method of hollow structure material, comprises the following steps:
1), take silicon grain as original material, with heating method realize the oxidation to silicon grain surface.Silicon grain is placed in to tubular type revolving burner and is heated to 1000 degrees Celsius, in this process, steam is constantly passed into accelerate oxidation rate.Silicon grain surface forms the oxide layer (silicon dioxide layer) of even thickness after high-temperature heating, obtains intermediate product A.Wherein, the thickness of oxide layer is controlled by adjusting the high-temperature heating time.
2), intermediate product A that step 1) is obtained joins in the tromethamine cushioning liquid that contains dopamine, the concentration of tromethamine cushioning liquid is 0.001M.The mass ratio of product A, dopamine and tromethamine cushioning liquid is 0.05:1, above-mentioned mixed solution is stirred, through the stirring of 24 hours, product A surface wraps last layer dopamine polymer, collect and dry in 110 degrees Celsius of vacuum environments by vacuum filtration, obtain product B.
3), by step 2) product B that obtains is placed on and in tubular type revolving burner, carries out carbonization; under the protection of Ar gas; be warming up to 250 degrees Celsius; heat 3 hours; be warming up to 1000 degrees Celsius, heat 1 hour, through above-mentioned heating process; the dopamine polymer on product B surface is converted into unsetting carbon-coating, obtains product C.
4), product C that step 3) is obtained is placed in the HF solution of 10%wt and reacts, until remove the silicon dioxide layer in indefinite form carbon silicon and silica dioxide granule, obtains the Si hollow structure material being wrapped by unsetting carbon C.
embodiment 3
The preparation method of hollow structure material, comprises the following steps:
1), take silicon grain as original material, with heating method realize the oxidation to silicon grain surface.Silicon grain is placed in to tubular type revolving burner and is heated to 1100 degrees Celsius, in this process, steam is constantly passed into accelerate oxidation rate.Silicon grain surface forms the oxide layer (silicon dioxide layer) of even thickness after high-temperature heating, obtains intermediate product A.Wherein, the thickness of oxide layer is controlled by adjusting the high-temperature heating time.
2), intermediate product A that step 1) is obtained joins in the tromethamine cushioning liquid that contains dopamine, the concentration of tromethamine cushioning liquid is 10M.The mass ratio of product A and dopamine is 50:1, above-mentioned mixed solution is stirred, and through the stirring of 24 hours, product A surface wrapped last layer dopamine polymer, collect and dry in 110 degrees Celsius of vacuum environments by vacuum filtration, obtain product B.
3), by step 2) product B that obtains is placed on and in tubular type revolving burner, carries out carbonization; under the protection of Ar gas; be warming up to 550 degrees Celsius; heat 1 hour; be warming up to 650 degrees Celsius, heat 5 hours, through above-mentioned heating process; the dopamine polymer on product B surface is converted into unsetting carbon-coating, obtains product C.
4), product C that step 3) is obtained is placed in the HF solution of 10%wt and reacts, until remove the silicon dioxide layer in indefinite form carbon silicon and silica dioxide granule, obtains the Si hollow structure material being wrapped by unsetting carbon C.
embodiment 4
1), take Ge particle as parent material, by Ge particle and water, ethanol and ammoniacal liquor mix (volume ratio of ammoniacal liquor is 80:20:1 for ethanol, water).In this mixed liquor, add tetraethyl orthosilicate.Stir after 12 hours, can obtain the Ge particle that SiO2 wraps, i.e. product A;
2) product A step 1) being obtained joins in the tromethamine cushioning liquid that contains dopamine, and the concentration of tromethamine cushioning liquid is 1M.The mass ratio of product A and dopamine is 30:1, above-mentioned mixed solution is stirred, and through the stirring of 24 hours, product A surface wrapped last layer dopamine polymer, collect and dry in 110 degrees Celsius of vacuum environments by vacuum filtration, obtain product B;
3), by step 2) product B that obtains is placed on and in tubular type revolving burner, carries out carbonization; under the protection of Ar gas; be warming up to 400 degrees Celsius; heat 2 hours; be warming up to 800 degrees Celsius, heat 2.5 hours, through above-mentioned heating process; the dopamine polymer on product B surface is converted into unsetting carbon-coating, obtains product C.Wherein, the time that is warming up to 400 degrees Celsius and 800 degrees Celsius is respectively 5 hours and 1.5 hours.
4), the product C obtaining is placed in to the HF solution of 10%wt, SiO2 reacts dissolved with HF, the Ge hollow structure material that obtains being wrapped by C.
embodiment 5
1), with LiMnO 2particle is parent material, utilizes the method for ald (ALD) at its plated surface last layer Al 2o 3;
2), product A that step 1) is obtained joins in the tromethamine cushioning liquid that contains dopamine, the concentration of tromethamine cushioning liquid is 5M.The mass ratio of product A, dopamine and tromethamine cushioning liquid is 40:1, above-mentioned mixed solution is stirred, and through the stirring of 24 hours, product A surface wrapped last layer dopamine polymer, collect and dry in 110 degrees Celsius of vacuum environments by vacuum filtration, obtain product B;
3), by step 2) product B that obtains is placed on and in tubular type revolving burner, carries out carbonization, under the protection of Ar gas, be warming up to 300 degrees Celsius, heat 2.5 hours, be warming up to 700 degrees Celsius, heat 3 hours, through above-mentioned heating process, the dopamine polymer on product B surface is converted into unsetting carbon-coating, obtains product C;
4), the product C preparing is placed in to 10%wt NaOH solution.Al 2o 3react dissolved with NaOH, the LiMnO that obtains being wrapped by C 2hollow structure material.
embodiment 6
Take Si particle as parent material, utilize the method for ald (ALD) to plate Al at Si particle surface successively 2o 3layer and TiO 2layer, obtains surface and is coated with Al 2o 3layer and TiO 2the Si particle of layer.The surface preparing is coated with to Al 2o 3layer and TiO 2the Si particle of layer is placed in 10%wt NaOH solution.Al 2o 3react dissolved with NaOH, obtain by TiO 2the Al hollow structure material wrapping.
embodiment 7
With LiCoO 2particle is parent material, utilizes the method for ald (ALD) successively at LiCoO 2particle surface plates Al 2o 3layer and TiO 2layer, obtains surface and is coated with Al 2o 3layer and TiO 2the LiCoO of layer 2particle.The surface preparing is coated with to Al 2o 3layer and TiO 2the LiCoO of layer 2particle is placed in 10%wt NaOH solution.Al 2o 3react dissolved with NaOH, obtain by TiO 2the LiMnO wrapping 2hollow structure material.
Hollow structure material of the present invention can be applied in the energy storage devices such as lithium ion battery, ultracapacitor, lithium-air battery, for improving the electric stable circulation performance of electrode material.
Except Si-C system, this hollow structure material also may be used on other systems.Concrete variation is derivative to be comprised:
1. material:
core:as the anode of lithium battery, except silicon, other active materials also can be used as the core of this hollow-core construction.For example Ge, Sn, SnO 2, Al, Sb, TiO 2and their alloy.As the negative electrode of lithium battery, LiCoO 2, LiFePO 4, LiMnO 2, LiNiO 2, LiMn 2o 4, LiCoPO 4, LiNi xco ymn 1-x-yo 2, LiNi xco yal zo 2, LiFe 2(SO4) 3, FeF 3can be used as core Deng material.
top layer shell material:except unsetting carbon, Al 2o 3, TiO 2, CdS, Fe 2o 3also can be used as wrapping of surface Deng material.
the preliminary treatment of material:active material can further improve its performance through doping.Dopant material comprises Ni, Ti, Cu, P etc.
structure:
size:the size of core can be low to moderate 1-20nm, 20-100nm, and 100-500nm, high to 100-500nm, 500-1000nm, 1-10um, 10-50um, 50-100um etc.
But the volume 0-10% of the voidage core between core and shell, 10-99%, 99%-500% etc. the thickness of top layer shell can reach 0-10nm, 10-50nm, 50-100nm etc.
synthetic method:
the synthetic method of nuclear material:buy except business, additive method also can be used to synthetic silicon or other active materials.Concrete grammar comprises hot CVD, plasmas-enhanced CVD, hot-wire CVD, physical vapor deposition (PVD), wetetching, combustion method, sol-gel process, solid-statereaction, coprecipitation, hydro thermal method etc.
the acquisition methods of oxide layer:oxide layer can obtain by high-temperature thermal oxidation or chemical oxidization method.Except being oxidized existing nuclear material, oxide layer also can be by obtaining at nuclear material plated surface oxide.The method that can be used for applying oxidn comprises chemical vapor deposition (CVD), plasmas-enhanced CVD, hot-wire CVD, physical vapor deposition (PVD), sputtering, evaporation, atomic layer deposition (ALD), spinning coating, sol-gel process, coprecipitation, hydro thermal method etc.
the preparation of shell material:the method that wraps of shell material comprises solution-based polymer coating, sputtering, atomic layer deposition, evaporation, coprecipitation, pyrolysis etc.

Claims (9)

1. a hollow structure material, is characterized in that: comprise core and shell, described core is arranged in described shell, between described core and shell, has space, and described core is silicon grain, and described shell is unsetting carbon shell.
2. hollow structure material as claimed in claim 1, is characterized in that:
As the anode of lithium battery, described silicon grain is by Ge particle, Sn particle, SnO 2particle, Al particle, Sb particle, TiO 2the alloying pellet of particle or above-mentioned material replaces;
As the negative electrode of lithium battery, described silicon grain is by LiCoO 2particle, LiFePO 4particle, LiMnO 2particle, LiNiO 2particle, LiMn 2o 4particle, LiCoPO 4particle, LiNi xco ymn 1-x-yo 2particle, LiNi xco yal zo 2particle, LiFe 2(SO4) 3particle or FeF 3particle replaces;
Described shell is by Al 2o 3layer, TiO 2layer, CdS layer or Fe 2o 3layer replaces.
3. the hollow structure material as described in claim 1 or 2 any one, is characterized in that: the diameter of described core is 1nm-100um, (0,500%) that the voidage between described core and shell is described Assessment of Nuclear Volume, and the thickness of described shell is (0,100nm).
4. a preparation method for hollow structure material, is characterized in that: comprise the following steps:
1), take silicon grain as original material, with heating method realize the oxidation to silicon grain surface, make the surface of silicon grain be coated with layer of silicon dioxide, obtain intermediate product A;
2), intermediate product A is joined in the tromethamine cushioning liquid that contains dopamine, above-mentioned mixed solution is stirred, until intermediate product A surface wraps last layer dopamine polymer, dry, obtain intermediate product B;
3), intermediate product B is placed on and in heating furnace, carries out carbonization, under argon shield, be warming up to 250-550 degree Celsius, heating 1-3 hour, be warming up to 650-1000 degree Celsius, heating 1-5 hour, through above-mentioned heating process, the dopamine polymer on intermediate product B surface is converted into unsetting carbon, obtains intermediate product C;
4), intermediate product C is placed in HF solution and is reacted,, until remove the silicon dioxide layer in intermediate product C, obtain hollow structure material.
5. the preparation method of hollow structure material as claimed in claim 4, it is characterized in that: the diameter that removes the silicon grain of silicon dioxide layer in the described hollow structure material obtaining in step 4) is 1nm-100um, the volume of described silicon dioxide layer be remove silicon dioxide layer silicon grain volume (0,500%), the thickness of unsetting carbon-coating is (0,100nm).
6. the preparation method of hollow structure material as claimed in claim 4, is characterized in that: in the heating process described in step 1), pass into steam.
7. the preparation method of hollow structure material as claimed in claim 4, is characterized in that: in step 3), under argon shield, be warming up to 400 degrees Celsius, heat 2 hours, be warming up to 800 degrees Celsius, heat 2.5 hours.
8. the preparation method of hollow structure material as claimed in claim 4, is characterized in that: step 2) in the concentration of tromethamine cushioning liquid be (0.001M, 10M), the mass ratio of intermediate product A and dopamine is 0.05-50:1.
9. a purposes for hollow structure material, is characterized in that, the purposes of the hollow structure material described in claim 1-3 any one in the cyclical stability of electrode that improves lithium battery, lithium ion battery or lithium-air battery.
CN201410025915.8A 2014-01-21 2014-01-21 Hollow structure material as well as preparation method and use thereof Pending CN103779546A (en)

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CN104900858A (en) * 2015-06-15 2015-09-09 中南大学 Preparation method for sodium-ion battery antimony/carbon anode composite material with yolk-shell structure
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CN104201006B (en) * 2014-08-15 2017-06-27 国家纳米科学中心 A kind of Preparation method and use of CNT/manganese dioxide hydridization electrode material for super capacitor
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CN104953122A (en) * 2015-06-30 2015-09-30 深圳清华大学研究院 Nanometer silicon and carbon composite negative electrode material and preparation method and lithium ion battery thereof
CN105206815A (en) * 2015-09-28 2015-12-30 清华大学 Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof
CN105206815B (en) * 2015-09-28 2017-11-14 清华大学 A kind of carbon coating Li4Ti5O12‑TiO2/ Sn nano composite materials and its preparation and application
CN105226260B (en) * 2015-10-19 2017-11-24 中南大学 A kind of preparation method of lithium ion battery silicon based anode material
CN105226260A (en) * 2015-10-19 2016-01-06 中南大学 A kind of preparation method of lithium ion battery silicon based anode material
CN105609867A (en) * 2015-10-22 2016-05-25 芜湖凯尔电气科技有限公司 High-capacity lithium ion battery
CN105406041A (en) * 2015-11-05 2016-03-16 盐城工学院 Hollow titanium oxide composite material, and preparation method and application thereof
CN105406041B (en) * 2015-11-05 2017-09-01 盐城工学院 A kind of hollow titanium composite material, preparation method and application
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US10424784B2 (en) 2016-10-28 2019-09-24 GM Global Technology Operations LLC Negative electrode including silicon nanoparticles having a carbon coating thereon
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CN107768650A (en) * 2017-10-25 2018-03-06 中国计量大学 Lithium ion battery negative material and preparation method thereof
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US10637048B2 (en) 2018-05-30 2020-04-28 GM Global Technology Operations LLC Silicon anode materials
CN109192937A (en) * 2018-07-26 2019-01-11 辽宁石油化工大学 A kind of preparation method of silicon-carbon cathode material
CN109873135A (en) * 2019-01-23 2019-06-11 广西大学 A kind of technique and its device preparing nanoscale core-shell structure carbon coating composite material
US11374218B2 (en) 2019-08-21 2022-06-28 GM Global Technology Operations LLC Multilayer siloxane coatings for silicon negative electrode materials for lithium ion batteries
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CN111029555A (en) * 2019-12-30 2020-04-17 中科廊坊过程工程研究院 Positive electrode material and preparation method and application thereof
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