CN109962214A - A kind of carbon nanometer layer coated Si negative electrode material and its preparation and application - Google Patents
A kind of carbon nanometer layer coated Si negative electrode material and its preparation and application Download PDFInfo
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- CN109962214A CN109962214A CN201711339205.2A CN201711339205A CN109962214A CN 109962214 A CN109962214 A CN 109962214A CN 201711339205 A CN201711339205 A CN 201711339205A CN 109962214 A CN109962214 A CN 109962214A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
The present invention relates to ion cathode material lithium technical fields, and in particular to a kind of carbon nanometer layer coated Si negative electrode material and preparation method thereof, the preparation method include the following steps: A, preparation carbon precursor；B, carbon silicon precursor is prepared；C, carbon nanometer layer coated Si negative electrode material is prepared.The carbon silicium cathode material of preparation is the nanometer chip architecture of porous carbon coating nano-silicon, and the silicon nano of cladding is distributed in carbon-coating surface.Clad structure greatly reduces the volume expansion of silicon；The porous structure of high porosity, which effectively alleviates silicon expansion, influences electrode structure；And carbon nanometer layer provides preferable conductive network.Method for coating of the present invention is easy, and raw material sources are extensive, and cheap, process conditions are easy to control, and operating cost is low, great industrial prospect.Compared to existing method for coating, have many advantages, such as that clad is uniform, cladding rate is fast.Carbon nanometer layer coated Si negative electrode material specific capacity of the invention is high, and cycle performance and high rate performance are excellent.
Description
Technical field
The present invention relates to ion cathode material lithium technical fields, and in particular to a kind of carbon nanometer layer coated Si negative electrode material and
Preparation method.
Background technique
Lithium ion battery has energy density height, self discharge as a kind of using very extensive energy storage device
Small, the advantages that operating voltage range is wide, memory-less effect, long service life, non-environmental-pollution, performance of lithium ion battery it is final
Deciding factor is electrode material, and wherein negative electrode material plays a crucial role the raising of performance of lithium ion battery.Mesh
The application of preceding negative electrode material is mainly based on conventional graphite material, but graphite specific capacity has been approached the theoretical value of 372mAh/g, difficult
Have the space of promotion, be unable to satisfy the demand of high-energy-density dynamic lithium battery, thus develop other novel anode materials to
It promotes lithium battery performance and has become negative electrode material research field hot spot.
The theoretical specific capacity of silicon is 4200mAh/g, and the voltage platform much higher than the specific capacity of graphite material, and silicon is slightly above
Graphite will not cause surface to analyse lithium in charging, and security performance is more preferable, and in addition silicon is from a wealth of sources, and storage is abundant, so silicon quilt
Think one of the novel anode material for most possibly substituting graphite.But using silicon as lithium ion battery negative material in the mistake of embedding lithium
Volume expansion is up to 300% in journey.The insertion abjection of lithium ion repeatedly, material gradually dusting cause structure to collapse in charge and discharge process
It collapses, eventually leads to electrode active material and collector is detached from, lose electrical contact, cycle performance of battery is caused to substantially reduce；In addition,
Due to this bulk effect, silicon is difficult to form stable solid electrolyte interface (SEI) film in the electrolytic solution；Along with electrode knot
The destruction of structure constantly forms new SEI film in the silicon face exposed, exacerbates corrosion and the capacity attenuation of silicon.
It mainly uses the methods of modified surface, doping, compound to be formed the modification of high capacity silicium cathode material at present to wrap
It covers or the system of high degree of dispersion, by improving the mechanical property of material, to alleviate in volume expansion during removal lithium embedded generates
Destruction of the stress to material structure, to improve its electrochemical cycle stability.Pass through organic carbon source surface aggregate
(CN103531760B, CN104466185A) or hydrothermal carbonization cladding to carbon silicium cathode be mostly monodispersed carbon silicon nanometer
Ball, though these materials can be improved in cyclicity, the electronics conduction between particle is extremely limited, and is imitated
Fruit is still not ideal enough, is unable to satisfy the performance requirement of high-performance power lithium-ion battery.
How clad structure does at present, has which type of problem (for documents) to contrast the present invention
The advantage of technical solution
Summary of the invention
The object of the invention is to provide a kind of effective lithium-ion electric to overcome the problems of the above-mentioned prior art
The method of pond carbon coating silicium cathode material can be substantially reduced the special capacity fade speed of carbon silicium cathode material, improve carbon silicium cathode
The cycle performance of material, while efficent electronic conduction pathway being provided, improve the high rate performance of battery.The present invention is using in detail below
What scheme was realized:
(1) polyalcohol and inorganic acid after mixing evenly and are heated and vacuumizes and brings it about esterification, amination will be contained
The dispersion liquid for closing object is added in gained reaction product, and heating brings it about salt-forming reaction after mixing again, obtains carbon precursor
Suspension:
(2) carbon precursor suspension obtained by step (1) is uniformly mixed with nano silicon oxide；
(3) by the resulting carbon silicon precursor of step (2) under an inert atmosphere high temperature cabonization and magnesiothermic reduction up to carbon silicium cathode.
The ratio of the amount of the substance of the polyalcohol described in step (1) and inorganic acid is 1:3-1:8；The inorganic acid and ammonia
The ratio of the amount of the substance of based compound is 5:1-1:1.
Solvent described in step (1) is water, methanol, ethyl alcohol, ethylene glycol or two kinds and two or more mixed liquors；It is described more
First alcohol is pentaerythrite, xylitol, one or more kinds of in sorbierite；The inorganic acid is boric acid, phosphoric acid, sulfuric acid, nitric acid
Middle one or more；The amino-compound is urea, melamine, cyanamide, one or more kinds of in amino acid.
Dispersion liquid mass concentration described in step (1) containing amino-compound is 3-50%.
The condition of esterification described in step (1) is to react 0.5-5h at 70-200 DEG C；Vacuum degree is 0.03-
0.2Mpa, the salt-forming reaction condition react 2-24h at a temperature of being 30-150 DEG C.
Nano silicon oxide described in step (2) is the mesoporous silicons such as 10nm-100nm silicon oxide ball, MCM-41, SBA-15, silicon
One or both of siliceous natural minerals such as diatomaceous earth.
Nano silicon oxide described in step (2) and the mass ratio of carbon precursor are 1:50-1:10.
Carbonization treatment condition described in step (3) are as follows: be warming up to 300-600 DEG C and keep 0.5-3h, continue to increase temperature
To 700-1100 DEG C, this temperature 0.5-3h is kept, is cooled to room temperature.
It is 2-10 DEG C/min that carbonization treatment condition described in step (3), which is with heating rate,
Inert gas described in step (3) is nitrogen, gaseous mixture one or two kinds of in argon gas.
Magnesium powder and the carbon-silicon compound mass ratio 1:2-5:1 after carbonization, heating in magnesiothermic reduction step described in step (3)
To 500-700 DEG C and 2-20h is kept, heating rate is 2-10 DEG C/min, is cooled to room temperature, and inert gas is hydrogen, in argon gas
One or two kinds of gaseous mixtures.By products therefrom 1M hydrochloric acid washing by soaking, the carbon silicium cathode material of drying.
Compared with prior art, carbon silicium cathode material prepared by the present invention is lamellar structure, the silicon nano point of cladding
It is distributed in carbon-coating surface.Clad structure greatly reduces the volume expansion of silicon；The gel structure of high porosity effectively alleviates
Silicon expansion influences electrode structure；And carbon nanometer layer provides preferable conductive network.Due to the protection of carbon coating layer, silicon material
Material gradually participates in electrochemical reaction in cyclic process, and cyclicity is obviously improved.And the method for the present invention is easy, operating cost
It is low, great industrial prospect.
Detailed description of the invention
Fig. 1: the scanning electron micrograph of silicium cathode material；
Fig. 2: the scanning electron micrograph of silicium cathode material；
Fig. 3: the transmission electron micrograph of silicium cathode material；
Fig. 4: the transmission electron micrograph of silicium cathode material.
Specific embodiment
Embodiment 1
6.8g pentaerythrite is weighed in flask, 29.40g phosphoric acid, stirring decompression (vacuum degree 0.1MPa), heating is added
To 120 DEG C, 1.5h is kept the temperature, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.It is added in another round-bottomed flask
120mL ethyl alcohol and 16.38g melamine, are sufficiently stirred 3h, and the pentaerythritol phosphate synthesized in upper step is poured into and is equipped with
In the melamine of alcohol dispersant, 80 DEG C are heated to, is stirred at reflux 6h, rotary evaporation obtains precursor, and 2g precursor and 200mg is straight
The silicon oxide ball of diameter 30nm is uniformly mixed, and mixture is put in quartz boat, under nitrogen atmosphere, the heating rate liter of 5 DEG C/min
Temperature keeps 0.5h to 350 DEG C, continues to be warming up to 950 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.
By the carbon-silicon compound 3:1 in mass ratio after magnesium powder and carbonization, it is warming up to 600 DEG C and keeps 3h, heating rate is 5 DEG C/min,
It is cooled to room temperature, inert gas is argon gas.By products therefrom 1M hydrochloric acid washing by soaking, the carbon silicium cathode material of drying.
Gained silicium cathode material is embedded in carbon nanometer layer by silicon nano as shown in Fig. 1 scanning electron microscope and is constituted.
Embodiment 2
6.8g pentaerythrite is weighed in flask, 29.40g phosphoric acid, stirring decompression (vacuum degree 0.1MPa), heating is added
To 120 DEG C, 1.5h is kept the temperature, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.It is added in another round-bottomed flask
120mL ethyl alcohol and 16.38g melamine, are sufficiently stirred 3h, and the pentaerythritol phosphate synthesized in upper step is poured into and is equipped with
In the melamine of alcohol dispersant, 80 DEG C are heated to, is stirred at reflux 6h, rotary evaporation obtains precursor, and 2g precursor and 100mg is straight
The silicon oxide ball of diameter 50nm is uniformly mixed, and mixture is put in quartz boat, under nitrogen atmosphere, the heating rate liter of 5 DEG C/min
Temperature keeps 0.5h to 350 DEG C, continues to be warming up to 950 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.
By the carbon-silicon compound 3:1 in mass ratio after magnesium powder and carbonization, it is warming up to 600 DEG C and keeps 3h, heating rate is 5 DEG C/min,
It is cooled to room temperature, inert gas is argon gas.By products therefrom 1M hydrochloric acid washing by soaking, the carbon silicium cathode material of drying.
Gained silicium cathode material is embedded in carbon nanometer layer by silicon nano as shown in Fig. 2 scanning electron microscope and is constituted.
Embodiment 3
6.8g pentaerythrite is weighed in flask, 29.40g phosphoric acid, stirring decompression (vacuum degree 0.1MPa), heating is added
To 120 DEG C, 1.5h is kept the temperature, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.It is added in another round-bottomed flask
120mL ethyl alcohol and 16.38g melamine, are sufficiently stirred 3h, and the pentaerythritol phosphate synthesized in upper step is poured into and is equipped with
In the melamine of alcohol dispersant, 80 DEG C are heated to, is stirred at reflux 6h, rotary evaporation obtains precursor, and 2g precursor and 100mg is straight
The silicon oxide ball of diameter 50nm is uniformly mixed, and mixture is put in quartz boat, under nitrogen atmosphere, the heating rate liter of 5 DEG C/min
Temperature keeps 0.5h to 350 DEG C, continues to be warming up to 950 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.
By the carbon-silicon compound 3:1 in mass ratio after magnesium powder and carbonization, it is warming up to 600 DEG C and keeps 3h, heating rate is 5 DEG C/min,
It is cooled to room temperature, inert gas is argon gas.By products therefrom 1M hydrochloric acid washing by soaking, the carbon silicium cathode material of drying.
Gained silicium cathode material is embedded in carbon nanometer layer by silicon nano as shown in Fig. 3 and 4 transmission electron microscopes and is constituted, and silicon is received
Rice corpuscles diameter is in 50nm or so.
Claims (10)
1. a kind of carbon silicon composite cathode material, it is characterised in that: be made of in carbon nanometer layer silicon nano, the silicon is received
The mass content of rice corpuscles is 20-80%, and the partial size of silicon nano is 10-100nm.
2. the preparation method of carbon silicon composite cathode material described in a kind of claim 1, it is characterised in that: include the following steps,
(1) polyalcohol and inorganic acid after mixing evenly and are heated and vacuumizes and brings it about esterification, amino-compound will be contained
Dispersion liquid be added gained esterification reaction product in, again after mixing heating bring it about salt-forming reaction, obtain carbon precursor
Suspension, it is dry to obtain carbon precursor；
(2) carbon precursor obtained by step (1) is uniformly mixed with nano silicon oxide；
(3) by step (2) resulting mixture under an inert atmosphere high temperature cabonization and magnesiothermic reduction up to carbon silicium cathode.
3. preparation method as claimed in claim 2, it is characterised in that:
The ratio of the amount of the substance of polyalcohol described in step (1) and inorganic acid is 2:1-1:8；The inorganic acid and amino-compound
Substance amount ratio be 5:1-1:5；
The solvent that dispersion liquid containing amino-compound described in step (1) uses for water, methanol, ethyl alcohol, ethylene glycol or two kinds and
Two or more mixed liquors；The polyalcohol is pentaerythrite, xylitol, one or more kinds of in sorbierite；It is described inorganic
Sour is one or more kinds of in boric acid, phosphoric acid, sulfuric acid, nitric acid；The amino-compound is urea, melamine, cyanamide, ammonia
It is one or more kinds of in base acid；
The dispersion liquid mass concentration containing amino-compound is 3-50%.
4. preparation method as claimed in claim 2, it is characterised in that: the condition of esterification described in step (1) is in 70-
0.5-5h is reacted at 200 DEG C；Vacuum degree is 0.03-0.2Mpa, and the salt-forming reaction condition reacts 2- at a temperature of being 30-150 DEG C
24h。
5. preparation method as claimed in claim 2, it is characterised in that: nano silicon oxide described in step (2) is 10nm-
One or more of the silicon oxide ball of 100nm, MCM-41, SBA-15；
Nano silicon oxide described in step (2) and the mass ratio of carbon precursor are 1:50-1:10.
6. preparation method as claimed in claim 2, it is characterised in that: carbonization treatment condition described in step (3) are as follows: from room temperature
It is warming up to 300-600 DEG C and keeps 0.5-3h, continue to increase temperature to 700-1100 DEG C, keep this temperature 0.5-3h, be cooled to
Room temperature.
7. preparation method as claimed in claim 6, it is characterised in that:
Carbonization treatment process described in step (3) with heating rate be 2-10 DEG C/min；
Inert atmosphere gases described in step (3) are nitrogen, gaseous mixture one or two kinds of in argon gas.
8. preparation method as described in claim 1, it is characterised in that:
Magnesium powder and the carbon-silicon compound mass ratio 1:2-5:1 after carbonization in magnesiothermic reduction step described in step (3), from room temperature liter
Temperature is to 500-700 DEG C and keeps 2-20h, and heating rate is 2-10 DEG C/min, is cooled to room temperature after magnesiothermic reduction, magnesiothermic reduction
Atmosphere is hydrogen, gaseous mixture one or two kinds of in argon gas.
9. preparation method as described in claim 1, it is characterised in that: by products therefrom hydrochloric acid washing by soaking, drying
Carbon silicon composite cathode material；Hydrochloric acid molar concentration used is 0.2-2mol/L.
10. carbon silicon composite cathode material application described in a kind of claim 1, it is characterised in that: the carbon silicium cathode is lithium ion
Battery cathode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110474034A (en) * | 2019-08-22 | 2019-11-19 | 陕西科技大学 | A kind of nitrogen mixes porous nano-sheet Si-C composite material and its preparation method and application |
| CN112582620A (en) * | 2020-12-14 | 2021-03-30 | 陕西科技大学 | Carbon-coated silicon nanoparticle material and preparation method and application thereof |
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| CN101826612A (en) * | 2009-03-06 | 2010-09-08 | 五邑大学 | Preparation method of lithium ion battery silicon-carbon cathode material |
| CN103346325A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
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| CN110474034A (en) * | 2019-08-22 | 2019-11-19 | 陕西科技大学 | A kind of nitrogen mixes porous nano-sheet Si-C composite material and its preparation method and application |
| CN112582620A (en) * | 2020-12-14 | 2021-03-30 | 陕西科技大学 | Carbon-coated silicon nanoparticle material and preparation method and application thereof |
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