CN104332594A - Silicon-based negative electrode material and preparation method and application thereof - Google Patents
Silicon-based negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicon-based negative electrode material and a preparation method and an application thereof, and belongs to the field of lithium ion battery negative electrode material. The silicon-based negative electrode material comprises graphene having a layered structure, nano silicon particles and nano metal particles, wherein the nano silicon particles and the nano metal particles are all embedded in the layered structure of the graphene. The nano silicon particles are all embedded in the layered structure of the graphene, and the graphene having the grid structure can bind the nano silicon particles in a relatively fixed space, so that the volume effect of a silicon material is effectively buffered, an SEI film is avoided from being continuously thickened, and the cycle stability of the negative electrode material is improved. At the same time, the nano metal particles are embedded in the layered structure of the graphene, so that the efficiency of electronic transmission is improved, the formation of higher junction resistance is avoided, the conductivity of the negative electrode material is improved, and then the cycle stability is improved.
Description
Technical field
The present invention relates to lithium ion battery negative material field, particularly a kind of silicon based anode material and its preparation method and application.
Background technology
Lithium battery (i.e. lithium ion battery) be a kind of with carbon element active material for negative pole, can the battery of discharge and recharge with what make positive pole containing the compound of lithium.Its charge and discharge process, is embedding and the deintercalation process of lithium ion: during charging, and lithium ion is from positive pole deintercalation, and by electrolyte and barrier film, embed negative pole, the lithium ion embedded in negative pole is more, and the charge specific capacity of battery is higher; Otherwise during electric discharge, lithium ion is from negative pole deintercalation, and by electrolyte and barrier film, embed positive pole, from negative pole, the lithium ion of deintercalation is more, and the specific discharge capacity of battery is higher.Visible, the charge-discharge performance of embedding lithium capacity (i.e. specific capacity) on battery of lithium cell cathode material has important impact.Graphitic conductive is good, has layer structure, the embedding of very applicable lithium ion and deintercalation, but its specific capacity is lower, is only 372mAh/g, causes the specific capacity of lithium battery lower.
And silica-base material has the height ratio capacity up to 4200mAh/g, but in the embedding of lithium ion and the process of deintercalation, there is very large bulk effect (cubical expansivity is up to 300%-400%) in this material, cause the efflorescence of silica-base material in charging and discharging lithium battery process and come off, such one side affects the connection between active material and collector, is unfavorable for electric transmission; Make solid electrolyte interface film (the solid electrolyte interface formed between silica-base material and electrolyte on the other hand, be called for short SEI) film progressive additive, be unfavorable for improving lithium battery capacity, cause the cycle performance of lithium battery sharply to decline.
Prior art (CN 102593418A) prepares carbon silicon composite cathode material by carbon and silicon are carried out compound, make to have the carbon of relative resilient structure and this space to cushion the bulk effect of silicon, improve the cycle performance of silicon, its step is as follows: (1) mixes: mixed with silica flour by organic carbon presoma, obtain the mixture of organic carbon presoma and silica flour; (2) coated: by said mixture high temperature cabonization in an inert atmosphere, to obtain the composite material of the tight coated Si of porous carbon layer; (3) corrode: remove the part silicon in the composite material of the tight coated Si of described porous carbon layer with corrosive liquid, obtain carbon silicon composite cathode material, in this carbon silicon composite cathode material, between carbon and silicon, there is space.
Inventor finds that prior art at least exists following problem:
The silicon based anode material that prior art provides easily forms higher junction resistance, causes its cyclical stability poor.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, provides good silicon based anode material of a kind of cyclical stability and its preparation method and application.Concrete technical scheme is as follows:
First aspect, embodiments provides a kind of silicon based anode material, comprising: have the Graphene of layer structure, silicon nanoparticle and nano-metal particle, and described silicon nanoparticle and described nano-metal particle are all embedded in the layer structure of described Graphene.
As preferably, described silicon based anode material comprises the composition of following mass percent: the Graphene 5-20% with layer structure, nano-metal particle 1-5%, and surplus is silicon nanoparticle.
Particularly, as preferably, described nano-metal particle is nano copper particle and/or nano-Ag particles.
Particularly, as preferably, the particle diameter of described silicon nanoparticle is 5-80nm.
Second aspect, embodiments provides a kind of above-mentioned silicon based anode material and is preparing the application in lithium ion battery.
The third aspect, embodiments provides a kind of preparation method of above-mentioned silicon based anode material, comprising:
Step a, silicon nanoparticle to be dissolved in the ethanolic solution of the Graphene containing layer structure, to stir, obtain the first mixed solution;
Step b, centrifugal treating is carried out to described first mixed solution, obtain the Graphene being embedded with nano-silicon, and the described Graphene being embedded with nano-silicon is washed;
Step c, the Graphene being embedded with nano-silicon after washing to be added in the solution containing slaine, stir, then in the described solution containing slaine, add hydrofluoric acid, make the reducing metal ions in described slaine become metal, obtain the second mixed solution;
Steps d, suction filtration process is carried out to described second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and the described Graphene being embedded with nano-silicon and nano metal is washed, dry process;
Step e, the Graphene being embedded with nano-silicon and nano metal described in dried to be calcined, obtain silicon based anode material.
Particularly, as preferably, in described step a, described in stir and to be realized by ultrasonic agitation or magnetic agitation.
Particularly, as preferably, in described step c, described metal salt solution is selected from the salting liquid of silver and/or copper.
Particularly, as preferably, in described step e, at the temperature of 250-500 DEG C, described calcining is carried out.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
The silicon based anode material that the embodiment of the present invention provides, by silicon nanoparticle is embedded in the layer structure of Graphene, silicon nanoparticle is strapped in relatively-stationary space by the Graphene with network, thus effectively cushion the bulk effect of silicon materials, avoid constantly thickening of SEI film, improve the cyclical stability of negative material.Meanwhile, by being embedded in the layer structure of Graphene by nano-metal particle, improve electric transmission efficiency, avoiding the formation of higher junction resistance, improve the conductivity of this negative material, and then improve the cyclical stability of this negative material.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the silicon based anode material that the embodiment of the present invention provides.
Reference numeral represents respectively:
1 Graphene,
2 silicon nanoparticles,
3 nano-metal particles.
Embodiment
For making technical scheme of the present invention and advantage clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
First aspect, embodiments provides a kind of silicon based anode material, and accompanying drawing 1 is the structural representation of this silicon based anode material.As shown in Figure 1, this silicon based anode material comprises: have the Graphene 1 of layer structure, silicon nanoparticle 2 and nano-metal particle 3, and silicon nanoparticle 2 and nano-metal particle 3 are all embedded in the layer structure of Graphene 1.
The silicon based anode material that the embodiment of the present invention provides, by silicon nanoparticle is embedded in the layer structure of Graphene, silicon nanoparticle is strapped in relatively-stationary space by the Graphene with network, thus effectively cushion the bulk effect of silicon materials, avoid constantly thickening of SEI film, improve the cyclical stability of negative material.Meanwhile, by being embedded in the layer structure of Graphene by nano-metal particle, improve electric transmission efficiency, avoiding the formation of higher junction resistance, improve the conductivity of this negative material.
Be understandable that, the structure of the Graphene described in the embodiment of the present invention is lamellar structure, it has at least two-layer graphene layer, silicon nanoparticle and nano-metal particle are distributed in the lamellar structure of Graphene, that is silicon nanoparticle and nano-metal particle are dispersed between adjacent graphene layer, and combine with graphene layer.
Further, embodiments provide a kind of preferred silicon based anode material, comprise the composition of following mass percent: the Graphene 5-20% with layer structure, nano-metal particle 1-5%, surplus is silicon nanoparticle.
Further, the mass percent of Graphene is preferably 10-15%, is more preferably 15%; The mass percent of nano-metal particle is preferably 3-5%, is more preferably 5%.
In order to improve the electric conductivity of prepared volume silicon based anode material, particularly, above-mentioned nano-metal particle is nano copper particle and/or nano-Ag particles.As preferably, the particle diameter of above-mentioned nano-metal particle is 10-60nm; The particle diameter of silicon nanoparticle is 5-80nm.
Second aspect, embodiments provides a kind of above-mentioned silicon based anode material and is preparing the application in lithium ion battery.That is embodiments provide a kind of lithium ion battery, this lithium ion battery comprises above-mentioned silicon based anode material.
Be understandable that, the lithium ion battery prepared by above-mentioned silicon based anode material has good cyclical stability and conductivity concurrently.
The third aspect, embodiments provides a kind of preparation method of above-mentioned silicon based anode material, and the method can be carried out at normal temperatures.Particularly, the method comprises:
Step 101, silicon nanoparticle to be dissolved in the ethanolic solution of the Graphene with layer structure, to stir, described silicon nanoparticle is embedded in the layer structure of described Graphene, obtains the first mixed solution.
Particularly, in step 101, make silicon nanoparticle dispersed by ultrasonic agitation or magnetic agitation and embed in the layer structure of Graphene.
The embodiment of the present invention does not do concrete restriction to the concentration of the ethanolic solution of above-mentioned Graphene, and its concentration is beneficial to make that silicon nanoparticle is dispersed is advisable wherein.
Step 102, centrifugal treating is carried out to the first mixed solution obtained in step 101, obtain the Graphene being embedded with nano-silicon, and the Graphene that this is embedded with nano-silicon is washed.
The Graphene being embedded with nano-silicon obtained in step 102 refers to silicon nanoparticle dispersion, is preferably evenly dispersed in the layer structure of Graphene, and is physically combined with graphene layer.
Particularly, clear water can be utilized to wash the Graphene being embedded with nano-silicon, to remove the impurity that it contains, avoid the chemical property of anticathode material to cause adverse effect.
Step 103, by washing after the Graphene being embedded with nano-silicon add in the solution containing slaine, stir, the metal ion in slaine is made to be dispersed in the layer structure of this Graphene, then contain in the solution of slaine add hydrofluoric acid to this, make above-mentioned reducing metal ions become metal, obtain the second mixed solution.
In step 103, the structural reducing metal ions of Graphene stratiform will be dispersed in by using hydrofluoric acid and become nano-metal particle, obtained metallic particles is combined with graphene layer.The amount of hydrofluoric acid is reduced completely to make metal ion, is preferably just reduced to suitable.The mass concentration of hydrofluoric acid preferably 10%.
Be understandable that, the combination of metallic particles and Graphene can rely on electrostatic adsorption to realize.
As preferably, in order to obtain the metallic particles of even-grained nanoscale, embodiment of the present invention metal salt solution used is selected from the salting liquid of silver and/or copper.For example, can be liquor argenti nitratis ophthalmicus, copper nitrate solution, copper citrate solution.
Be understandable that, other metals, such as manganese, iron, aluminium, magnesium etc. also can be applied to the present invention.
Step 104, suction filtration process is carried out to the second mixed solution that step 103 obtains, obtains the Graphene being embedded with nano-silicon and nano metal, and the Graphene being embedded with nano-silicon and nano metal is washed, dry process.
In step 104, washing process can be carried out, to remove undesirable impurity that Graphene contains by using clear water.Drying process can be carried out by spraying dry or the heat drying at 60-80 DEG C.
Step 105, the dried Graphene being embedded with nano-silicon and nano metal to be calcined, obtain the silicon based anode material expected.
By calcining the Graphene being embedded with nano-silicon and nano metal, increase silicon nanoparticle and nano-metal particle and Graphene in conjunction with dynamics, improve the stability of this negative material.As preferably, at 250-500 DEG C, at the temperature of preferred 300-450 DEG C, carry out described calcining.
Below further the present invention will be described by specific embodiment.
Specification raw materials used in following examples is as follows:
Graphene model GR-003 is purchased from Suzhou Heng Qiu Graphene Science and Technology Ltd.;
Silicon nanoparticle model YFG01-N30 is purchased from Shanghai Yun Fu nanosecond science and technology Co., Ltd.
Embodiment 1
Present embodiments provide a kind of silicon based anode material, comprise the composition of following mass percent: Graphene 5%, nano-metal particle 2%, silicon nanoparticle 93%.
Above-mentioned silicon based anode material is prepared by following preparation method:
According to the mass ratio of composition each in above-mentioned negative material, Graphene is dissolved in ethanolic solution, after stirring, adds silicon nanoparticle again, ultrasonic agitation 1h, make silicon nanoparticle be embedded on Graphene, obtain the first mixed solution.Centrifugal treating is carried out to this first mixed solution, obtains the Graphene being embedded with nano-silicon, and utilize clear water to wash 3 times.The Graphene being embedded with nano-silicon after washing is added in liquor argenti nitratis ophthalmicus, stirs 0.5h, and then add the hydrofluoric acid that mass concentration is 10% in this liquor argenti nitratis ophthalmicus, make silver ion reduction become nano-Ag particles, obtain the second mixed solution.Suction filtration process is carried out to the second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and to utilizing clear water to carry out washing 3 times to it, then at 50 DEG C, carry out drying.At the temperature of 250 DEG C, the dried Graphene being embedded with nano-silicon and nano metal is calcined, obtain the silicon based anode material expected.
Embodiment 2
Present embodiments provide a kind of silicon based anode material, comprise the composition of following mass percent: Graphene 10%, nano-metal particle 1%, silicon nanoparticle 89%.
Above-mentioned silicon based anode material is prepared by following preparation method:
According to the mass ratio of composition each in above-mentioned negative material, Graphene is dissolved in ethanolic solution, after stirring, adds silicon nanoparticle again, ultrasonic agitation 1.5h, make silicon nanoparticle be embedded on Graphene, obtain the first mixed solution.Centrifugal treating is carried out to this first mixed solution, obtains the Graphene being embedded with nano-silicon, and utilize clear water to wash 2 times.The Graphene being embedded with nano-silicon after washing is added in copper nitrate solution, stirs 0.5h, and then add the hydrofluoric acid that mass concentration is 10% in this copper nitrate solution, make copper ion be reduced into nano copper particle, obtain the second mixed solution.Suction filtration process is carried out to the second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and to utilizing clear water to carry out washing 2 times to it, then at 45 DEG C, carry out drying.At the temperature of 300 DEG C, the dried Graphene being embedded with nano-silicon and nano metal is calcined, obtain the silicon based anode material expected.
Embodiment 3
Present embodiments provide a kind of silicon based anode material, comprise the composition of following mass percent: Graphene 15%, nano-metal particle 3%, silicon nanoparticle 82%.
Above-mentioned silicon based anode material is prepared by following preparation method:
According to the mass ratio of composition each in above-mentioned negative material, Graphene is dissolved in ethanolic solution, after stirring, adds silicon nanoparticle again, ultrasonic agitation 2h, make silicon nanoparticle be embedded on Graphene, obtain the first mixed solution.Centrifugal treating is carried out to this first mixed solution, obtains the Graphene being embedded with nano-silicon, and utilize clear water to wash 4 times.The Graphene being embedded with nano-silicon after washing is added in liquor argenti nitratis ophthalmicus, stirs 1.5h, and then add the hydrofluoric acid that mass concentration is 10% in this liquor argenti nitratis ophthalmicus, make silver ion reduction become nano-Ag particles, obtain the second mixed solution.Suction filtration process is carried out to the second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and to utilizing clear water to carry out washing 4 times to it, then at the temperature of 60 DEG C, carry out drying.At the temperature of 450 DEG C, the dried Graphene being embedded with nano-silicon and nano metal is calcined, obtain the silicon based anode material expected.
Embodiment 4
Present embodiments provide a kind of silicon based anode material, comprise the composition of following mass percent: Graphene 20%, nano-metal particle 5%, silicon nanoparticle 75%.
Above-mentioned silicon based anode material is prepared by following preparation method:
According to the mass ratio of composition each in above-mentioned negative material, Graphene is dissolved in ethanolic solution, after stirring, adds silicon nanoparticle again, ultrasonic agitation 2.5h, make silicon nanoparticle be embedded on Graphene, obtain the first mixed solution.Centrifugal treating is carried out to this first mixed solution, obtains the Graphene being embedded with nano-silicon, and utilize clear water to wash 4 times.The Graphene being embedded with nano-silicon after washing is added in copper citrate solution, stirs 1.5h, and then add the hydrofluoric acid that mass concentration is 10% in this copper citrate solution, make copper ion be reduced into nano copper particle, obtain the second mixed solution.Suction filtration process is carried out to the second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and to utilizing clear water to carry out washing 2 times to it, then at the temperature of 70 DEG C, carry out drying.At the temperature of 500 DEG C, the dried Graphene being embedded with nano-silicon and nano metal is calcined, obtain the silicon based anode material expected.
Embodiment 5
The silicon based anode material that the present embodiment utilizes embodiment 1-4 to provide prepares lithium ion battery, and tests the chemical property of this lithium ion battery.Wherein, the preparation method of this battery is as follows:
Each silicon based anode material in embodiment 1-4 is mixed according to the mass ratio of 80:10:10 with conductive agent acetylene black and binding agent sodium alginate, then be coated in uniformly on Copper Foil with scraper, vacuumize 24 hours at 100 DEG C, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
In the process that the button cell prepared is detected, when being less than or equal to 10 times, adopt the discharge mechanism of 0.1C, when 10 times to 30 times, adopt the discharge mechanism of 0.2C, when 30 times to 50 times, adopt the discharge mechanism of 0.5C, when 50 times to 100 times, adopt the discharge mechanism of 1C, after 100 times, adopt the discharge mechanism of 2C.Experimental result is as shown in table 1:
The electrochemical property test table of table 1 lithium ion battery
As shown in Table 1, the silicon based anode material prepared by the method utilizing the embodiment of the present invention above-mentioned is to prepare lithium ion battery, and its cyclical stability of gained lithium ion battery is good, has excellent chemical property.The method that the embodiment of the present invention provides is simple, easy to operate, is convenient to large-scale industrial application.
The foregoing is only preferred embodiment of the present invention, not in order to limit the scope of the invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a silicon based anode material, comprising: have the Graphene of layer structure, silicon nanoparticle and nano-metal particle, and described silicon nanoparticle and described nano-metal particle are all embedded in the layer structure of described Graphene.
2. silicon based anode material according to claim 1, is characterized in that, described silicon based anode material comprises the composition of following mass percent: the Graphene 5-20% with layer structure, nano-metal particle 1-5%, and surplus is silicon nanoparticle.
3. silicon based anode material according to claim 2, is characterized in that, described nano-metal particle is nano copper particle and/or nano-Ag particles.
4. silicon based anode material according to claim 3, is characterized in that, the particle diameter of described silicon nanoparticle is 5-80nm.
5. the silicon based anode material described in an any one of claim 1-4 is preparing the application in lithium ion battery.
6. a preparation method for silicon based anode material according to claim 1, comprising:
Step a, silicon nanoparticle to be dissolved in the ethanolic solution of the Graphene containing layer structure, to stir, obtain the first mixed solution;
Step b, centrifugal treating is carried out to described first mixed solution, obtain the Graphene being embedded with nano-silicon, and the described Graphene being embedded with nano-silicon is washed;
Step c, the Graphene being embedded with nano-silicon after washing to be added in the solution containing slaine, stir, then in the described solution containing slaine, add hydrofluoric acid, make the reducing metal ions in described slaine become metal, obtain the second mixed solution;
Steps d, suction filtration process is carried out to described second mixed solution, obtains the Graphene being embedded with nano-silicon and nano metal, and the described Graphene being embedded with nano-silicon and nano metal is washed, dry process;
Step e, the Graphene being embedded with nano-silicon and nano metal described in dried to be calcined, obtain silicon based anode material.
7. method according to claim 6, is characterized in that, in described step a, described in stir and to be realized by ultrasonic agitation or magnetic agitation.
8. method according to claim 7, is characterized in that, in described step c, the described solution containing slaine is the salting liquid of silver and/or copper.
9. the method according to any one of claim 6-8, is characterized in that, in described step e, at the temperature of 250-500 DEG C, carries out described calcining.
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Cited By (4)
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|---|---|---|---|---|
| CN105680012A (en) * | 2016-01-22 | 2016-06-15 | 奇瑞汽车股份有限公司 | Silicon-based anode material and preparation method and application thereof |
| CN106941160A (en) * | 2017-03-27 | 2017-07-11 | 中国科学院宁波材料技术与工程研究所 | A kind of silver-colored carbon nano-hybrid material of the silicon containing Silver nanorod and its preparation method and application |
| CN106941156A (en) * | 2017-03-17 | 2017-07-11 | 中国科学院宁波材料技术与工程研究所 | Silver-colored carbon nano-hybrid material of a kind of silicon and its preparation method and application |
| CN108183220A (en) * | 2017-12-28 | 2018-06-19 | 新余学院 | A kind of lithium battery tertiary composite negative pole material and preparation method thereof |
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| CN106941160A (en) * | 2017-03-27 | 2017-07-11 | 中国科学院宁波材料技术与工程研究所 | A kind of silver-colored carbon nano-hybrid material of the silicon containing Silver nanorod and its preparation method and application |
| CN106941160B (en) * | 2017-03-27 | 2019-06-11 | 中国科学院宁波材料技术与工程研究所 | A kind of silicon silver carbon nano-hybrid material and its preparation method and application containing Silver nanorod |
| CN108183220A (en) * | 2017-12-28 | 2018-06-19 | 新余学院 | A kind of lithium battery tertiary composite negative pole material and preparation method thereof |
| CN108183220B (en) * | 2017-12-28 | 2021-03-19 | 新余学院 | Ternary composite negative electrode material of lithium battery and preparation method of ternary composite negative electrode material |
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