CN107195896B - A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature - Google Patents
A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature Download PDFInfo
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- CN107195896B CN107195896B CN201710222528.7A CN201710222528A CN107195896B CN 107195896 B CN107195896 B CN 107195896B CN 201710222528 A CN201710222528 A CN 201710222528A CN 107195896 B CN107195896 B CN 107195896B
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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
- H01M4/38—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention relates to a kind of preparation methods that silicium cathode material is synthesized using conductive metal nano particle as carrier low temperature, it is characterized by: using conductive metal nano particle as carrier, organosilicon hydrolyzation deposits silica, it mixes, heat-treat with metal, low melting point salt again, coated polymer, washing and drying obtains silicium cathode material；Conductive metal nano particle be Nanometer Copper, nano silver, Nanoscale Iron, nanometer bismuth, nanometer tin, nano nickel, nanometer cobalt, nanometer indium, nano-titanium it is one or more；Reducing metal is one of alloy of lithium, potassium, calcium, rubidium, sodium, strontium, barium, lanthanum and above-mentioned metal or a variety of；Low melting point salt is one of gallium, germanium, tin, aluminium, the villaumite of magnesium, bromide and villiaumite or a variety of；Polymer is one of derivative of polyaniline, polypyrrole, polythiophene and above-mentioned polymer or a variety of；The molar ratio (1~5) of silicon and conductive metal: 1；Silicon: reducing metal: the molar ratio of low melting point salt is 1: (2~5): (1~20)；The molar ratio of silicon and polymer precursor is (5~30): 1.The negative electrode material has good chemical property, has a good application prospect in field of lithium ion battery.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to one kind is using conductive metal nano particle as carrier low temperature
Synthesize the preparation method of silicium cathode material.
Background technique
Elemental silicon has many advantages, such as to store up lithium energy density height (theoretical capacity is up to 3580mA h/g), rich reserves, right and wrong
Often there is the lithium ion battery negative material of application prospect.But there are volume change during simple substance poorly conductive, removal lithium embedded is big for silicon
The defects of, cause silicon that can not be widely applied because of chemical property difference.Currently, scientific research personnel uses nano material, porous structure
Alleviate alleviation volume change, the conduction of increase silicon materials of the silicon in charge and discharge process with the methods of the carbon for being introduced into high conductivity
Property, to improve the cycle performance of silicon materials.But nanosizing and porous structure result in the reduction of material volume specific energy density, and
Preparation method is generally complicated, at high cost, limits its commercial applications.
SiOx material is a kind of silicium cathode material of better performances, and most widely used a kind of silicon materials at present.Reason
By the study found that Li is embedded into SiOx, it will form multiple compounds, these lithium silicon compounds become Si negative electrode volume expansion
Buffer strip, inhibits the volume expansion of silicium cathode, to improve the cycle performance of SiOx material.Patent 1 (CN105789577A,
A kind of preparation method and the silicium cathode material of lithium ion battery silicium cathode material) to aoxidize sub- silicon as raw material, hydroxylating, mixed
Graphite, high-temperature calcination acquisition silicium cathode material are closed, the chemical property of silicium cathode material is effectively increased.Patent 2
(CN105406050A, one kind meeting silicium cathode material, preparation method and purposes) using nano-silicon as raw material, passes through high temperature coated Si
Oxide and metal composite layer, again high temperature coated with conductive carbon-coating；The silicium cathode material capacity is higher than 1500mAh/g, 300 circulations
Capacity is maintained at 90% or more afterwards.
Obviously, the electrochemistry capacitance and cycle performance for improving SiOx are the passes for realizing SiOx electrode material commercial applications
Key, current research also obtain gratifying achievement.But energy consumption is high and generates large quantity of exhaust gas pollution environment for high-temperature calcination, virtually
Increase the preparation cost of SiOx electrode material.
Summary of the invention
It is an object of that present invention to provide a kind of systems that silicium cathode material is synthesized using conductive metal nano particle as carrier low temperature
Preparation Method overcomes the defect of existing technology of preparing, improves the chemical property of silicium cathode material.For achieving the above object,
The technical scheme is that a kind of preparation method that silicium cathode material is synthesized using conductive metal nano particle as carrier low temperature,
It is characterized by: using conductive metal nano particle as carrier, organosilicon hydrolyzation deposits silica, then with metal, low melting point salt
Mixing, thermal reduction, coated polymer, washing and drying obtain silicium cathode material；Conductive metal nano particle is Nanometer Copper, nanometer
Silver, Nanoscale Iron, nanometer bismuth, nanometer tin, nano nickel, nanometer cobalt, nanometer indium, nano-titanium it is one or more；Reducing metal be lithium,
Potassium, calcium, rubidium, sodium, strontium, barium, lanthanum and above-mentioned metal one of alloy or a variety of；Low melting point salt is gallium, germanium, tin, aluminium, magnesium
One of villaumite, bromide and villiaumite or a variety of；Polymer is polyaniline, polypyrrole, polythiophene and above-mentioned polymer
One of derivative is a variety of；The molar ratio (1~5) of silicon and conductive metal: 1；Silicon: reducing metal: mole of low melting point salt
Than being 1: (2~5): (1~20)；The molar ratio of silicon and polymer is (5~20): 1；One kind is to carry with conductive metal nano particle
Body hypothermia synthesis silicium cathode material preparation method include:
1) conductive nano-particles for weighing certain mass are dispersed in aqueous solutions of organic solvent, and surfactant is added, and are surpassed
1~20h of sound；
Wherein, organic solvent is one kind or several of the aldehydes of C1~C8, carboxylic acids, alcohols and above-mentioned organic matter derivative
Kind；The volume ratio of organic matter and water is (0.1~10): 1；
2) product that the ethanol solution of organosilicon is instilled to step 1), stirs 1~40h；Temperature is controlled at 10~100 DEG C；
Wherein, organosilicon is the one or more of esters of silicon acis, silane, silicon chloride, silicon bromide and above-mentioned organic matter derivative；
3) by the separation of the product of step 2), drying, mixed with metal and low melting point salt, be put into container, vacuumize, close,
In 200~500 DEG C of 2~40h of placement；
4) product of step 3) is put into hydrochloric acid solution, impregnates 5~60h；Separation, deionized water washing, drying；
5) product of step 4) is put into alcohol water blend, a certain amount of polymeric precursor is added, at the uniform velocity 2~5h of stirring；
Then initiator is added, stirring is stood, filtering, vacuum drying, obtains silicium cathode material.
Compared with other silicium cathode materials, the invention patent is had the advantages that
1) silicium cathode material technology of the present invention is simple and convenient to operate, and is conducive to industrialized production.
2) silicium cathode material preparation condition of the present invention is mild, and low energy consumption.
3) present invention uses metal nanoparticle for carrier deposit Si oxide, improves the electric conductivity of silicon, network-like to lead
Electric polymer provides enough spaces for silicium cathode expansion, so silicium cathode material prepared by the present invention has good electrochemistry
The charge/discharge capacity of performance, 50mA electric current, material is greater than 700mAh/g.
Specific embodiment
In order to further understand the content, features and effects of the present invention, hereby lifting following embodiment, detailed description are as follows:
Embodiment 1
A kind of ingredient design of silicium cathode material:
1) Nanometer Copper, 0.01mol；Ethyl orthosilicate, 0.02mol；Lithium metal, 0.04mol；Aluminium chloride, 0.04mol；Benzene
Amine, 0.002mol；
2) nano silver, 0.01mol；Silicon tetrachloride, 0.02mol；Magnesium metal, 0.04mol；Lithium chloride, 0.06mol；Pyrroles,
0.003mol；
3) nanometer tin, 0.01mol；Dichlorosilane, 0.02mol；Metallic aluminium, 0.04mol；Calcirm-fluoride, 0.06mol；Pyrroles,
0.003mol；
A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature:
1) nano-metal particle for weighing certain mass is dispersed in ethanol water, and Surfactant CTAB is added, and is surpassed
Sound 5h；The volume ratio of ethyl alcohol and water is 9: 1；
2) product that the ethanol solution of organosilicon is instilled to step 1), stirs 10h；Temperature is controlled at 40 DEG C；
3) by the separation of the product of step 2), drying, mixed with metal and low melting point salt, be put into container, vacuumize, close,
In 250 DEG C of placement 15h；
4) product of step 3) is put into hydrochloric acid solution, impregnates 5h；Separation, deionized water washing, drying, obtain SiOx/
Nano metal negative electrode material；
5) product of step 4) is put into alcohol water blend, a certain amount of polymeric precursor is added, at the uniform velocity 2~5h of stirring；
Then initiator is added, stirring is stood, filtering, vacuum drying, obtains silicium cathode material.
The silica-base material particle size is tiny, and porous structure is presented；When for negative electrode of lithium ion battery；After 100 circulations,
50mA discharge capacity is greater than 700mAh/g.
Embodiment 2
A kind of ingredient design of silicium cathode material:
4) Nanometer Copper, 0.01mol；Silicon tetrachloride, 0.01mol；Lithium metal, 0.02mol；Aluminium chloride, 0.04mol；Aniline,
0.001mol；
5) Nanometer Copper, 0.01mol；Silicon tetrachloride, 0.03mol；Magnesium metal, 0.07mol；Lithium chloride, 0.06mol；Pyrroles,
0.002mol；
6) Nanometer Copper, 0.01mol；Silicon tetrachloride, 0.04mol；Metallic aluminium, 0.12mol；Magnesium bromide, 0.06mol；Aniline,
0.0015mol；
A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature:
1) nano-metal particle for weighing certain mass is dispersed in ethanol water, and Surfactant CTAB is added, and is surpassed
Sound 10h；The volume ratio of ethyl alcohol and water is 5: 1；
2) product that the ethanol solution of organosilicon is instilled to step 1), stirs 5h；Temperature is controlled at 60 DEG C；
3) by the separation of the product of step 2), drying, mixed with metal and low melting point salt, be put into container, vacuumize, close,
In 300 DEG C of placement 5h；
4) product of step 3) is put into hydrochloric acid solution, impregnates 10h；Separation, deionized water washing, drying, obtain SiOx/
Nano metal negative electrode material；
5) product of step 4) is put into alcohol water blend, a certain amount of polymeric precursor is added, at the uniform velocity 2~5h of stirring；
Then initiator is added, stirring is stood, filtering, vacuum drying, obtains silicium cathode material.
The silica-base material particle size is tiny, and porous structure is presented；When for negative electrode of lithium ion battery；After 100 circulations,
50mA discharge capacity is greater than 700mAh/g.
Embodiment 3
Is operated with embodiment 1
A kind of ingredient design of silicium cathode material:
7) Nanoscale Iron, 0.01mol；Silicon tetrachloride, 0.01mol；Lithium metal, 0.02mol；Aluminium chloride, 0.04mol；Aniline,
0.001mol；
8) nano-titanium, 0.01mol；Silicon tetrachloride, 0.03mol；Magnesium metal, 0.07mol；Lithium chloride, 0.06mol；Pyrroles,
0.001mol；
9) Nanometer Copper, 0.01mol；Silicon tetrachloride, 0.04mol；Metal rubidium, 0.12mol；Magnesium bromide, 0.06mol；Poly- pair
Chloroaniline, 0.001mol；
10) nano nickel, 0.01mol；Silicon tetrachloride, 0.01mol；Lithium metal, 0.02mol；Aluminium chloride, 0.04mol；Poly- neighbour
Methylaniline, 0.001mol；
11) nanometer cobalt, 0.01mol；Silicon tetrachloride, 0.03mol；Magnesium metal, 0.07mol；Lithium chloride, 0.06mol；Between poly-
5-trifluoromethylaniline, 0.002mol；
12) nanometer indium, 0.01mol；Silicon tetrachloride, 0.04mol；Lanthanoid metal, 0.12mol；Magnesium bromide, 0.06mol；It is poly-
(1- methylene -2- methyl naphthalene)-N- pyrroles, 0.0015mol；
13) nanometer bismuth, 0.01mol；Silicon tetrachloride, 0.04mol；Metal rubidium, 0.12mol；Magnesium bromide, 0.06mol；Poly- 4-
(N- ethyl -1,8- naphthalimide) N- pyrroles,
The silica-base material particle size is tiny, and porous structure is presented；When for negative electrode of lithium ion battery；After 100 circulations,
50mA discharge capacity is greater than 700mAh/g.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (1)
1. a kind of preparation method for synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature, it is characterised in that: with
Conductive metal nano particle is carrier, and organosilicon hydrolyzation deposits silica, then mixes, heat-treats with metal, low melting point salt, is wrapped
Polymer is covered, washing and drying obtains silicium cathode material；Conductive metal nano particle is Nanometer Copper, nano silver, Nanoscale Iron, nanometer
Bismuth, nanometer tin, nano nickel, nanometer cobalt, nanometer indium, nano-titanium it is one or more；Reducing metal is strontium, barium, lanthanum and above-mentioned
One of alloy of metal is a variety of；Low melting point salt is one of gallium, germanium, tin, aluminium, the bromide of magnesium and villiaumite or a variety of；
Polymer is one of derivative of polyaniline, polypyrrole, polythiophene and above-mentioned polymer or a variety of；Silicon and conductive metal
Molar ratio (1~5): 1；Silicon: reducing metal: the molar ratio of low melting point salt is 1: (2~5): (1~20)；Before silicon and polymer
The molar ratio for driving body is (5~30): 1；A kind of preparation synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature
Method includes:
1) conductive nano-particles for weighing certain mass are dispersed in aqueous solutions of organic solvent, addition surfactant, and ultrasound 1~
20h；Wherein, organic solvent is the one or more of the aldehydes of C1~C8, carboxylic acids, alcohols and above-mentioned organic matter derivative；Have
The volume ratio of machine object and water is (0.1~10): 1；
2) product that the ethanol solution of organosilicon is instilled to step 1), stirs 1~40h；Temperature is controlled at 10~100 DEG C；
Wherein, organosilicon is the one or more of esters of silicon acis, silane and above-mentioned organosilicon derivates；
3) it by product separation, the drying of step 2), is mixed with metal and low melting point salt, is put into container, vacuumizes, close, 200
~500 DEG C of 2~40h of placement；
4) product of step 3) is put into hydrochloric acid solution, impregnates 5~60h；Separation, deionized water washing, drying；
5) product of step 4) is put into alcohol water blend, a certain amount of polymeric precursor is added, at the uniform velocity 2~5h of stirring；Then
Initiator is added, stirring is stood, filtering, vacuum drying, obtains silicium cathode material.
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| CN109817925A (en) * | 2019-01-24 | 2019-05-28 | 广东凯金新能源科技股份有限公司 | Lithium ion secondary battery Si oxide composite negative pole material and preparation method |
| CN112234183B (en) * | 2020-10-14 | 2021-10-26 | 中国计量大学 | Preparation method for in-situ synthesis of conductive metal/silicon/polymer-based negative electrode material |
| CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
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