CN106654220A - Preparation method of high-capacity carbon-silicon composite negative material - Google Patents
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Abstract
The invention discloses a preparation method of a high-capacity carbon-silicon composite negative material. The method comprises the following steps: firstly crushing leftover wastes of photovoltaic monocrystalline silicon wafers via a crushing machine, finely grinding the leftover wastes via a sand grinder, sieving, removing impurities by using an acid solution, then ball milling the obtained monocrystalline silicon powder and a graphite material in a solvent to obtain precursor powder, adding the precursor powder into an asphalt organic solution, uniformly dispersing, drying after the solvent is completely volatilized, and pre-sintering and calcining to obtain the high-capacity carbon-silicon composite negative material. Through the preparation method of the high-capacity carbon-silicon composite negative material, the leftover wastes of the photovoltaic monocrystalline silicon wafers are used as silicon sources, a layer of carbon material is coated on the surface of the monocrystalline silicon/ graphite precursor powder, and a buffering layer is provided for volume expansion of silicon, so that conductivity and cycle stability of the material are improved; by adopting the preparation disclosed by the invention, the waste resources are reused; the preparation method is simple and environmentally friendly, and is low in cost; the prepared high-capacity carbon-silicon composite negative material has excellent cycle performance and high rate capability, can meet the usage requirements on lithium-ion energy storage and power batteries, and has a good application prospect.
Description
Technical field
The present invention is applied to lithium ion battery negative material and electrochemical field, is related to a kind of compound with high power capacity carbon silicon
The preparation method of negative material.
Background technology
With the development and the continuous consumption of world energy sources of human society, solve energy crisis and thing followed environment is dirty
Dye such as haze, greenhouse effects have become the problem of a globalization.Therefore increasing researcher is devoted to exploring new
The green energy resource of type.From early 1990s, lithium ion battery technology obtains important breakthrough, and is widely used in each neck
Domain, serves considerable effect in daily life.Therefore, develop height ratio capacity, high-specific-power, low cost,
The high performance lithium ion battery tool of green non-pollution is of great significance.
On October 26th, 2016, what Ministry of Industry and Information issued《Energy-conservation and new-energy automobile Technology Roadmap》Middle proposition：" new forms of energy
Automobile is increasingly becoming main product, and automobile industry is tentatively realized that motorized makes the transition, is expected to the year two thousand twenty new-energy automobile year sales volume
Reach 2,100,000, to 2025 and the year two thousand thirty, year sales volume will be up to 5,250,000,15,200,000.Pure electric vehicle power electricity is required simultaneously
Pond monomer specific energy will reach 350Wh/kg, and system specific energy reaches 250Wh/kg, and monomer energy density reaches 650Wh/L, is
System energy density reaches 320Wh/L, meets more than 300km BEV application demands ".However, business-like silicon/carbon/graphite in lithium ion batteries
(372mAh/g) negative material can only achieve in actual applications 300～340mAh/g, and its capacity has been difficult lifting, it is impossible to
Meet the demand.And according to the introduction in research report of Sanford C.Bernstein companies of the U.S., the Model 3 of tesla
Battery technology take the lead in employing the carbon silicon composite cathode material that silicon content is 10%, specific capacity is up to 500mAh/g.From industry
The battery technology of tesla achieves important breakthrough from the perspective of change, and this has also directly driven domestic lithium electricity industry in carbon silicon
Using upper exploration and research.In numerous negative materials, Si materials have very high theoretical specific capacity (4200mAh/g),
Therefore suffer from researchers widely to study, but the electric conductivity of Si materials is poor and produces in charge and discharge process huge
Volume Changes (>=300%), easy efflorescence the problems such as, seriously constrain Si as the exploitation of lithium ion battery negative material and should
With.
Improve at present the method for carbon silicon composite cathode material mainly using nano-silicon and and oxidation Asia silicon respectively with carbon materials
Material is combined to reach the purpose of high-energy-density, high rate capability and good cyclical stability.Wherein, Xu [Xu Q,
Li J Y,Sun J K,et al.Watermelon‐Inspired Si/C Microspheres with Hierarchical
Buffer Structures for Densely Compacted Lithium‐Ion Battery Anodes[J]
.Advanced Energy Materials, 2016.] and Mingseong [Mingseong K, Sujong C, Jiyong M, et
al.Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy
lithium-ion batteries[J].Nature Energy,2016,1:16113.] etc. researcher adopts different methods
The carbon-silicon composite material of cladded type, embedded type is prepared, the stability for making electrode material is greatly improved.This structure sets
Count using nano Si and provide high capacity as active material, C brings huge as dispersion phase, buffering Si in charge and discharge process
Volume Changes, so that it is guaranteed that the structure of material is not destroyed, and improve Si negative materials and collector in charge and discharge process
Make electrical contact with the problem that poor, capacity is decayed rapidly, cycle performance is poor.Patent CN101244814A and patent CN101710617B are disclosed
By carrying out compound negative material using nano-silicon and material with carbon element, although the cycle performance of material has obtained certain carrying
Height, but materials show has gone out a relatively low reversible capacity, and the high cost of nano-silicon is loaded down with trivial details with experiment preparation process
It is unfavorable for its industrial applications.
The present invention improves its electric conductivity by the use of the leftover bits of photovoltaic monocrystalline silicon piece as silicon source by addition graphite,
Again in monocrystalline silicon/one layer of material with carbon element of graphite precursor powder Surface coating, the volumetric expansion for silicon provides a cushion, so as to
Improve the electric conductivity and cyclical stability of material.The method that the present invention prepares carbon silicium cathode material, not only realizes waste and old resource
Recycling, simple production process are environmentally friendly, with low cost, and the product degree of crystallinity for obtaining is high, even particle size distribution.Present invention system
Standby carbon silicium cathode material has excellent cycle performance and good high rate performance, can meet lithium-ion energy storage and electrokinetic cell
Use requirement, have a good application prospect.
The content of the invention
For the volumetric expansion of silicon based anode material, efflorescence causes inducing capacity fading serious, and the problems such as cycle performance difference,
The present invention provides a kind of preparation method of high power capacity carbon silicon composite cathode material.
The technical scheme is that：
A kind of preparation method of high power capacity carbon silicon composite cathode material, the silicon content of the negative material is 1～10%, is adopted
Silicon source is the leftover bits of photovoltaic monocrystalline silicon piece, and simple production process, environmental protection are with low cost, its preparation method include as
Lower step：
(1) by the leftover bits Jing crusher in crushing of photovoltaic monocrystalline silicon piece, sand mill fine grinding, screening is removed with acid solution
Miscellaneous, gained monocrystalline silica flour and graphite material ball milling in a solvent is dried to obtain precursor powder after ball milling at 60～100 DEG C；
(2) asphalt powder is dissolved in solvent, 30～60min of uniform stirring, then step (1) gained forerunner is added to it
Body powder, dispersed with stirring is uniform, 30～60min of ultrasound；After the completion of reaction, treat that solvent volatilization is complete, be transferred to vacuum drying chamber
60～100 DEG C of 10～12h of drying；
(3) step (2) products therefrom is placed in tube furnace into first pre-burning to calcine again, that is, obtains high power capacity carbon silicon composite cathode
Material.
Further, the screening adopts the screen cloth of 400～800 mesh, and silica flour particle diameter is between 0.05～0.5 μm.
Further, the acid solution is one or two in hydrochloric acid solution or sulfuric acid solution.
Further, the graphite material be crystalline flake graphite, spherical natural graphite, the one kind in Graphene or expanded graphite
Or it is two or more.
Further, step (1) solvent is one or more in methyl alcohol, ethanol, propyl alcohol or isopropanol.
Further, the rotating speed of the ball milling is 200～600rpm.
Further, monocrystalline silica flour and the mass ratio of graphite material are 0.1～1.
Further, the pitch is coal tar asphalt, sulfonated gilsonite, asphalt, mesophase pitch or bitumen
One or more.
Further, step (2) solvent is quinoline, pyridine, tetrahydrofuran, toluene, benzene, hexamethylene, normal heptane, stone
One or more in oily ether or dimethylbenzene.
Further, the graphite material in step (2) precursor powder and the mass ratio of pitch are 0.125～2.
Further, pre-burning and calcining is carried out under protective atmosphere, and the protective atmosphere is the gaseous mixture of argon gas and hydrogen
Body, wherein, the volume accounting of argon gas is 80～99%, and hydrogen is 1～20%.
Further, calcined temperature is 300～400 DEG C, and burn-in time is 1～3h；Calcining heat is 700～900 DEG C, is forged
The burning time is 1～5h；Pre-burning and calcining are heated up using staged, and its heating rate is 1～5 DEG C/min.
The present invention has the following technical effect that：
(1) present invention adopts high temperature solid-state method, synthesis technique is simple, safe and reliable, low production cost, yield high,
Applicability is wide, be easy to industrialized production.
(2) present invention makes waste and old resource realize recycling by the use of the leftover bits of photovoltaic monocrystalline silicon piece as silicon source, passes through
Add graphite to improve its electric conductivity, then be the volume of silicon in monocrystalline silicon/one layer of material with carbon element of graphite precursor powder Surface coating
Expansion provides a cushion, so as to improve the electric conductivity and cyclical stability of material.Compared with other silicon based anode materials, this
Material has that energy density is higher, cycle life is longer and high rate performance is more excellent, can reach power lithium-ion battery big
Multiplying power, the use requirement of fast charging and discharging, in electric automobile and hybrid vehicle and energy storage field good answering is respectively provided with
Use prospect.
Description of the drawings
Fig. 1 is the XRD of the gained composite negative pole material of embodiment 1.
Fig. 2 is the first charge-discharge curve of the gained composite negative pole material of embodiment 1.
Fig. 3 is cycle performance figure of the gained composite negative pole material of embodiment 1 under the current density of 0.2C and 0.5C.
Fig. 4 is the high rate performance curve map of the gained composite negative pole material of embodiment 1.
Fig. 5 schemes for the SEM of the gained composite negative pole material of embodiment 1.
Specific embodiment
The present invention is further described by the following examples, so that those skilled in the art more fully understand this
It is bright, but the present invention is not limited to following examples.
Experimental technique in following embodiments, if no special instructions, is conventional method.
Embodiment 1
(1) under normal temperature, the leftover bits of a certain amount of photovoltaic monocrystalline silicon piece are crossed after 500 eye mesh screens, with 1mol/L's
H2SO4Solution removal of impurities, using ethanol as solvent, by monocrystalline silica flour and crystalline flake graphite 1 is pressed:Ball milling is carried out after 6 mass ratio mixing,
Rotating speed is 400rpm, and precursor powder is dried to obtain at 60 DEG C after ball milling；
(2) after is ground mesophase pitch powder, in being dissolved in pyridine, uniform stirring 45min, then by obtained by step (1)
Precursor powder is added and is uniformly dispersed in mesophase solution, ultrasonic 30min.Crystalline flake graphite and mesophase wherein in precursor powder
The mass ratio of pitch is 2：1.After the completion of reaction, at room temperature, treat that solvent volatilization is complete, be transferred to 80 DEG C of dryings of vacuum drying chamber
10h；
(3) step (2) products therefrom is placed according to volume ratio, argon gas 95%, hydrogen be 5% atmosphere in 400 DEG C
Pre-burning 1h, 3h is sintered in 900 DEG C, and heating rate is 3 DEG C/min.Room temperature is naturally cooled to, the height that a kind of silicon content is 6% is obtained
Capacity carbon silicon composite cathode material.
Fig. 1 is the XRD of the carbon silicium cathode material that the present embodiment gained has high power capacity.It can be seen that the material
The diffraction maximum of material is sharp, and degree of crystallinity is high.The carbon silicium cathode material with high power capacity synthesized in the present embodiment is assembled into button
Battery, with 1-METHYLPYRROLIDONE (NMP) as solvent, by the high power capacity carbon silicon composite cathode material synthesized in the present embodiment with it is poly-
Vinylidene (PVDF), acetylene black press 7：2：1 mass ratio is well mixed and is coated on Copper Foil, makes cathode pole piece, then with
Lithium piece is positive pole, is assembled into lithium ion battery.Under measuring room temperature, its specific volume that discharges first under the conditions of 0.1C, 0.01～1.5V
Amount is up to 634mAh/g；Under the conditions of 0.2C, 0.01～1.5V through 100 times circulation after capacity be 579mAh/g, 200 times circulation
Afterwards capacity still has 517mAh/g, sees Fig. 3.And under the current density of 0.5C, capacity still has 420mAh/ after 200 circulations
G, is shown in Fig. 3.It is back to 0.1C again under the current density condition of 0.1C, 0.2C, 0.5C, 1C, 2C and 5C, capacity still has 599mAh/
g.Electro-chemical test shows that the carbon silicium cathode material obtained by the present embodiment has higher capacity and preferable high rate performance, its times
Rate performance is shown in Fig. 4.
Embodiment 2
(1) under normal temperature, the leftover bits of a certain amount of photovoltaic monocrystalline silicon piece are crossed after 400 eye mesh screens, with the HCl of 1mol/L
After solution removal of impurities, using isopropanol as solvent, monocrystalline silica flour and Graphene are pressed into 1:Ball milling is carried out after 3 mass ratio mixing, is turned
Speed is 500rpm, and precursor powder is dried to obtain at 80 DEG C after ball milling.
(2) after by sulfonated gilsonite powder mull, in being dissolved in tetrahydrofuran solvent, uniform stirring 30min, then by step
(1) gained precursor powder is added and is uniformly dispersed in sulfonated gilsonite solution, ultrasonic 60min.Wherein Graphene in precursor powder
It is 1 with the mass ratio of sulfonated gilsonite:2.After the completion of reaction, at room temperature, treat that solvent volatilization is complete, be transferred to vacuum drying chamber
100 DEG C are dried 12h.
(3) step (2) products therefrom is placed according to volume ratio, argon gas 90%, hydrogen be 10% atmosphere in 400 DEG C
Pre-burning 1h, 1h is sintered in 900 DEG C, and heating rate is 5 DEG C/min.Room temperature is naturally cooled to, the Gao Rong that silicon content is 8.5% is obtained
The carbon silicium cathode material of amount.
Lithium ion battery is made according to method same as Example 1, electro-chemical test shows：0.1C, 0.01～
First discharge specific capacity is 707mAh/g in 1.5V voltage ranges；Hold Jing after 200 circulations under the conditions of 0.2C, 0.01-1.5V
Measure as 493mAh/g.Under 0.1C, the multiplying power of 0.2C, 0.5C, 1C, 2C, its specific discharge capacity be respectively 707mAh/g,
561mAh/g, 492mAh/g, 453mAh/g, 401mAh/g.
Embodiment 3
(1) under normal temperature, the leftover bits of a certain amount of photovoltaic monocrystalline silicon piece are crossed after 600 eye mesh screens, with 1mol/L's
H2SO4After solution removal of impurities, using methyl alcohol as solvent, monocrystalline silica flour and expanded graphite are pressed into 1:Ball is carried out after 4 mass ratio mixing
Mill, rotating speed is 600rpm, and precursor powder is dried to obtain at 80 DEG C after ball milling.
(2) after by asphalt powder mull, in being dissolved in cyclohexane solvent, uniform stirring 45min, then by step (1)
Gained precursor powder is added and is uniformly dispersed in asphalt solution, ultrasonic 30min.Wherein in precursor powder expanded graphite with
The mass ratio of asphalt is 1：1.25.After the completion of reaction, at room temperature, treat that solvent volatilization is complete, be transferred to vacuum drying chamber
80 DEG C are dried 10h.
(3) step (2) products therefrom is placed according to volume ratio, argon gas 80%, hydrogen be 20% atmosphere in 400 DEG C
Pre-burning 1h, 3h is sintered in 900 DEG C, and heating rate is 3 DEG C/min.Room temperature is naturally cooled to, the high power capacity that silicon content is 9% is obtained
Carbon silicium cathode material.
Make lithium ion battery according to method same as Example 1, electro-chemical test shows, 0.1C, 0.01～
First discharge specific capacity is 747.62mAh/g in 1.5V voltage ranges；200 circulations of Jing under the conditions of 0.2C, 0.01-1.5V
Afterwards, its capacity is 491mAh/g, shows good cycle performance.
Embodiment 4
(1) under normal temperature, the leftover bits of a certain amount of photovoltaic monocrystalline silicon piece are crossed after 500 eye mesh screens, with the HCl of 1mol/L
After acid solution removal of impurities, with methyl alcohol and ethanol with volume ratio as 1：1 is solvent, and monocrystalline silica flour and spherical graphite are pressed into 1：1 matter
Amount ratio carries out ball milling after being well mixed, and rotating speed is 500rpm, and precursor powder is dried to obtain at 100 DEG C after ball milling.
(2) after is ground powdered coal tar pitch, in being dissolved in xylene solvent, uniform stirring 30min, then by step
(1) gained precursor powder is added and is uniformly dispersed in coal tar asphalt solution, ultrasonic 40min.Wherein scale in precursor powder
Graphite is 1 with the mass ratio of coal tar asphalt：8.After the completion of reaction, treat that solvent evaporation is complete, be transferred to 100 DEG C of vacuum drying chamber
It is dried 12h.
(3) step (2) products therefrom is placed according to volume ratio, argon gas 95%, hydrogen be 5% atmosphere in 400 DEG C
Pre-burning 1h, 3h is sintered in 800 DEG C, and heating rate is 5 DEG C/min.Room temperature is naturally cooled to, the Gao Rong that silicon content is 6.5% is obtained
The carbon silicium cathode material of amount.
Lithium ion battery is made according to method same as Example 1, electro-chemical test shows：0.1C, 0.01～
First discharge specific capacity is 751mAh/g in 1.5V voltage ranges；Under the conditions of 0.2C, 0.01～1.5V Jing after 200 circulations,
Its capacity is 496.4mAh/g, shows good cycle performance.
Claims (10)
1. a kind of preparation method of high power capacity carbon silicon composite cathode material, it is characterised in that the silicon content of the negative material is 1～
10%, the silicon source for being adopted for photovoltaic monocrystalline silicon piece leftover bits, preparation method comprises the steps：
(1) by the leftover bits Jing crusher in crushing of photovoltaic monocrystalline silicon piece, acid solution removal of impurities, institute are used in sand mill fine grinding, screening
Monocrystalline silica flour and graphite material ball milling in a solvent, be dried to obtain precursor powder at 60～100 DEG C after ball milling；
(2) asphalt powder is dissolved in solvent, 30～60min of uniform stirring, then step (1) gained precursor is added to it
End, dispersed with stirring is uniform, 30～60min of ultrasound, after the completion of reaction, treats solvent volatilization completely, be transferred to vacuum drying chamber 60～
100 DEG C of 10～12h of drying；
(3) step (2) products therefrom is placed in tube furnace into first pre-burning to calcine again, that is, obtains high power capacity carbon silicon composite cathode material
Material.
2. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：The screening
Using the screen cloth of 400～800 mesh, silica flour particle diameter is between 0.05～0.5 μm.
3. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：The acidity
Solution is one or two in hydrochloric acid solution or sulfuric acid solution.
4. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：The graphite
Material is crystalline flake graphite, spherical natural graphite, one or more in Graphene or expanded graphite.
5. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：The monocrystalline
Silica flour is 0.1～1 with the mass ratio of graphite material.
6. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：The pitch
One or more for coal tar asphalt, sulfonated gilsonite, asphalt, mesophase pitch or bitumen.
7. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：Step (1)
The solvent is one or more in methyl alcohol, ethanol, propyl alcohol or isopropanol；Step (2) solvent is quinoline, pyrrole
One or more in pyridine, tetrahydrofuran, toluene, benzene, hexamethylene, normal heptane, petroleum ether or dimethylbenzene.
8. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：Step (2)
Graphite material and the mass ratio of pitch are 0.125～2 in precursor powder.
9. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：Pre-burning and forge
Burning is carried out under protective atmosphere, and the protective atmosphere is the mixed gas of argon gas and hydrogen, wherein, the volume accounting of argon gas is 80
～99%, hydrogen is 1～20%.
10. the preparation method of high power capacity carbon silicon composite cathode material according to claim 1, it is characterised in that：Pre-burning temperature
Spend for 300～400 DEG C, burn-in time is 1～3h；Calcining heat is 700～900 DEG C, and calcination time is 1～5h；Pre-burning and forge
Burn and heated up using staged, its heating rate is 1～5 DEG C of min-1。
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| CN111211315A (en) * | 2020-02-26 | 2020-05-29 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
| CN111326723A (en) * | 2020-02-26 | 2020-06-23 | 宁夏博尔特科技有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
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| CN114180548A (en) * | 2021-11-12 | 2022-03-15 | 江苏大学 | Preparation method of silicon-carbon composite negative electrode material and lithium storage application |
| CN114975959A (en) * | 2022-06-22 | 2022-08-30 | 厦门大学 | Method for preparing silicon/carbon composite anode material by utilizing photovoltaic industry line cutting waste silicon |
| CN116598465A (en) * | 2023-06-19 | 2023-08-15 | 深圳光风新能源科技创新中心有限公司 | High-rate lithium battery negative electrode material and preparation method thereof |
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