CN109054447A - A kind of preparation method of humic acid charcoal-silica two-phase compounded mix - Google Patents

A kind of preparation method of humic acid charcoal-silica two-phase compounded mix Download PDF

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CN109054447A
CN109054447A CN201810972101.3A CN201810972101A CN109054447A CN 109054447 A CN109054447 A CN 109054447A CN 201810972101 A CN201810972101 A CN 201810972101A CN 109054447 A CN109054447 A CN 109054447A
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humic acid
silica
charcoal
phase
silica solution
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杨世诚
孙琦
张玉龙
谌伦建
薛晓晓
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Henan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Abstract

A kind of preparation method of humic acid charcoal-silica two-phase compounded mix, described method includes following steps: a, the silica solution that humic acid quality 0% ~ 30% is added into the humic acid after drying, add water, handled by wet ball grinding, is dried to obtain humic acid-silica solution mixture；B, by humic acid-silica solution mixture in N2Charing process is carried out under conditions of 800 ~ 1200 DEG C under atmosphere, obtains humic acid charcoal-silica two-phase compound；C, modifying agent is added to humic acid charcoal-silica two-phase compound, wet ball grinding is modified, modified humic acid charcoal-silica two-phase compounded mix product is obtained, wherein the additive amount of the modifying agent is humic acid charcoal-silica two-phase compounded mix quality 2% ~ 10%.The present invention replaces the petroleum of increasingly reduction as carbon source using humic acid, replaces organosilicon as silicon source using cheap silica solution, improves the utilization added value of humic acid and silica solution, reduces environmental pollution caused by carbon black or the production of carbon silicon dual phase filler.

Description

A kind of preparation method of humic acid charcoal-silica two-phase compounded mix
Technical field
The present invention relates to functional powder Material Fields, through charcoal after mixing more particularly, to a kind of humic acid with silica solution Change, modified obtained silica dioxide granule is evenly distributed on carbon-silicon two-phase compounded mix surface method.
Technical background
It is reported that white carbon black carbon black is used cooperatively the rolling resistance that tire tread glue can be effectively reduced, lag damage is reduced It loses, reduces fuel consumption, reduce exhaust emissions, be known as environmentally protective tire (Hu little Long silica/silicon alkane filled rubber Crosslinking and enhancing [J] rubber and plastic utilization of resources of system, 2004 (5): 35-43；Zhao Tongjian, Lao Bangsheng accord with new nanometers of nothing Research [J] elastomer of research (II) nanosized SiO_2/native rubber composite material of machine particle reinforcement natural rubber, 2007, 17 (6): 63-68.).Carbon black is strongly depend on petroleum industry, and seriously polluted, and white carbon black production cost is too high, energy consumption It is huge, therefore development and application are at low cost, environmentally protective, the good filler of reinforcing effect becomes in the important research of rubber materials Hold (preparation of State of Zhao's jade tablet rubber matrix nanocomposites and performance study [D] Shanghai University, 2011.).Cabot carbon-silicon Dual phase filler is obtained by pyrolysis petroleum and organosilicon, and this novel filler has different specific surface areas, structural And dioxide-containing silica.In the associativity of filler and rubber, the mixed fillers of Cabot dual phase filler and same carbon silicone content Compared to higher associativity, lower filler-filler interacts, while needing a small amount of modifier treatment (MURPHY L J, WANG M J, MAHMUD K. Carbon—Silica Dual Phase Filler: Part V. Nano- Morphology [J] Rubber Chemistry & Technology, 2000,73 (1): 25-38.).It is double as carbon-silicon Phase filling, although Cabot dual phase filler has so excellent performance, it still relies on stone increasingly deficient on the earth Oily resource is as carbon source.Humic acid is that most commonly used natural organic macromolecule material is distributed in ball ecological environment, has storage Amount is big, from a wealth of sources, while humic acid surfaces active function groups rich in, mainly carboxyl, alcoholic extract hydroxyl group, phenolic hydroxyl group, quinone Base, the oxygen-containing functional groups such as methoxyl group and enol base, therefore activity and the higher (humic acid in Zhang Jingjing municipal sludge of hydrophily Extraction process and its performance study [D] Zhengzhou University, 2016；BRUNETTI G, PLAZA C, CLAPP C E, et al. Compositional and functional features of humic acids from organic amendments and amended soils in Minnesota, USA[J]. Soil Biology & Biochemistry, 2007,39(6):1355-1365；TANAKA T, ZHANG Z. Functional Groups and Reactivity of Size-fractionated Aldrich Humic Acid[J]. Thermochimica Acta, 2012,532 (6): 60-64.).There are a large amount of activated silica hydroxy functional groups in silica solution, therefore using humic acid as carbon source, silicon is molten Glue is as silicon source, thus instead of petroleum and organosilicon in Cabot dual phase filler, by mechanochemical treatment, make humic acid with Silica solution is combined into carbon-silicon biphase mixture during mixing, and further charing and modification obtain humic acid Charcoal-silica solution carbon silicon dual phase filler.
Humic acid surfaces contain a large amount of active function groups, a large amount of active silicone hydroxyl are also contained in silica solution, the two is in machine Under the action of tool chemical force, chemical change can occur, generation is effectively combined, and forms humic acid-silica solution mixture.It passes through again Charing and modification are crossed, humic acid charcoal-compound dual phase filler of silica is obtained.The dual phase filler of this carbon silicon, can portion Divide and replace the application of carbon black and more advanced carbon black or white carbon black in rubber product, improves the application performance of rubber composite material, New thinking and approach are provided for the preparation of carbon silicon dual phase filler.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of humic acid charcoal-silica two-phase compounded mix. This method is on the basis of existing carbon black-white carbon black dual phase filler research, and using humic acid as carbon source, silica solution is silicon source, It is prepared using ball milling mixing-this simple technique of anaerobic charing-ball milling modification a kind of with high structure-activity and compatibility The compound functional reinforcement powder body material of humic acid charcoal-silica two-phase.Significantly improve the physics of rubber composite material Mechanical performance has widened thinking for the exploitation of carbon silicon dual phase filler, reduces brought environment in the production of carbon silicon dual phase filler Pollution.
The purpose of the present invention can be realized by following technique measures:
Humic acid charcoal of the invention-silica two-phase compounded mix preparation method includes the following steps: a, to after drying Silica solution is added in humic acid, and wherein the additional amount of silica solution is the 0% ~ 30% of humic acid quality, adds water, at wet ball grinding Reason, is dried to obtain humic acid-silica solution mixture；B, by humic acid-silica solution mixture in N2At 800 ~ 1200 DEG C under atmosphere Under conditions of carry out charing process, obtain humic acid charcoal-silica two-phase compound；C, double to humic acid charcoal-silica Modifying agent is added in phase compound, and wet ball grinding is modified, obtains modified humic acid charcoal-silica two-phase compounded mix and produces Product, wherein the additive amount of the modifying agent is humic acid charcoal-silica two-phase compounded mix quality 2% ~ 10%.
Modifying agent described in step b of the present invention be derived from silane coupling agent silicon 69, Aluminate, titanate esters, hexa methyl silazane, Any one in neopelex, cetyl trimethylammonium bromide or polyethylene glycol.
Beneficial effects of the present invention are as follows:
The present invention uses humic acid for carbon source, and silica solution is silicon source, and through ball-milling treatment, humic acid and silica solution are evenly dispersed, Under the effect of mechanochemistry power, humic granulates reduce, and active function groups are released effectively, the high activity functional group in humic acid It is effectively combined with the active silicone hydroxyl generation in silica solution, forms humic acid-silica solution mixture.During charing, take off Except the active function groups in part humic acid-silica solution compound particles, the stability of filler is improved, while being reduced due to function Particle agglomeration phenomenon caused by mass contg is excessively high improves the dispersibility between the grindability and particle of charing particle.To humic acid Modifying agent is added in charcoal-silica two-phase compound, and ball milling modification further makes the granularity refinement of particle, connects in particle surface Branch modifying agent, further increases particle dispersion and hydrophobicity, exists to improve humic acid charcoal-silica two-phase compounded mix Dispersibility and compatibility in rubber matrix, significantly improve the comprehensive performance of composite material.The raw material sources of the preparation method Extensively, cheap, simple production process, environmental pollution is small, has good industrial production application prospect.
Detailed description of the invention
Fig. 1 is the SEM photograph of humic acid charcoal.
Fig. 2 is the SEM photograph that humic acid charcoal fills butadiene-styrene rubber composite material.
Fig. 3 is humic acid charcoal-silica two-phase compounded mix SEM photograph.
Fig. 4 is the SEM photograph that humic acid charcoal-silica two-phase compounded mix fills butadiene-styrene rubber composite material.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1(silica solution additive amount is 0, prepares humic acid charcoal)
Firstly, dry humic acid is added water in the ball mill, ball milling ground after humic acid, obtaining granularity after drying is d98=14.5 μm of humic acid, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, keep the temperature 1h, Humic acid charcoal is obtained, 5% silane coupling agent silicon 69 is added, wet ball grinding is modified, obtains humic acid carbon filling material.Altogether using melting Mixed method, according to formula NS, zinc oxide, fatty acid, filler, sulphur, the ratio (mass parts, phr) of each ingredient is 100:1: Humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, butadiene-styrene rubber composite material are made by 3:1:50:1.75.Mechanical property is such as Shown in table 1.
5%) embodiment 2(silica solution additive amount is
Firstly, the silica solution of mass ratio 5% is added to dry humic acid, add water in the ball mill, ball milling obtains humic acid-silicon Collosol intermixture, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, 1h is kept the temperature, obtains humic 5% silane coupling agent silicon 69 is added in sour charcoal-silica two-phase compound, and wet ball grinding is modified, obtains humic acid charcoal-dioxy SiClx dual phase filler.Using the method for melt blending, according to formula NS, zinc oxide, fatty acid, filler, sulphur, the ratio of each ingredient Example (mass parts, phr) is 100:1:3:1:50:1.75, and humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, butylbenzene is made Glue composite material.Mechanical property is as shown in table 1.
10%) embodiment 3(silica solution additive amount is
Firstly, the silica solution of mass ratio 10% is added to dry humic acid, add water in the ball mill, ball milling obtains humic acid-silicon Collosol intermixture, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, 1h is kept the temperature, obtains humic 5% silane coupling agent silicon 69 is added in sour charcoal-silica two-phase compound, and wet ball grinding is modified, obtains humic acid charcoal-dioxy SiClx dual phase filler.Using the method for melt blending, according to formula NS, zinc oxide, fatty acid, filler, sulphur, the ratio of each ingredient Example (mass parts, phr) is 100:1:3:1:50:1.75, and humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, butylbenzene is made Glue composite material.Mechanical property is as shown in table 1.
25%) embodiment 4(silica solution additive amount is
Firstly, the silica solution of mass ratio 25% is added to dry humic acid, add water in the ball mill, ball milling obtains humic acid-silicon Collosol intermixture, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, 1h is kept the temperature, obtains humic 5% silane coupling agent silicon 69 is added in sour charcoal-silica two-phase compound, and wet ball grinding is modified, obtains humic acid charcoal-dioxy SiClx dual phase filler.Using the method for melt blending, according to formula NS, zinc oxide, fatty acid, filler, sulphur, the ratio of each ingredient Example (mass parts, phr) is 100:1:3:1:50:1.75, and humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, butylbenzene is made Glue composite material.Mechanical property is as shown in table 1.
Embodiment 5(hexa methyl silazane)
Firstly, the silica solution of mass ratio 5% is added to dry humic acid, add water in the ball mill, ball milling obtains humic acid-silicon Collosol intermixture, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, 1h is kept the temperature, obtains humic 5% hexa methyl silazane is added in sour charcoal-silica two-phase compound, and wet ball grinding is modified, obtains humic acid charcoal-titanium dioxide Silicon dual phase filler.Using the method for melt blending, according to formula NS, zinc oxide, fatty acid, filler, sulphur, the ratio of each ingredient (mass parts, phr) is 100:1:3:1:50:1.75, and humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, butadiene-styrene rubber is made Composite material.Mechanical property is as shown in table 1.
Embodiment 6(neopelex)
Firstly, the silica solution of mass ratio 5% is added to dry humic acid, add water in the ball mill, ball milling obtains humic acid-silicon Collosol intermixture, then in N2Under atmosphere, 800 DEG C of roastings are warming up to the heating rate of 20 DEG C/min, 1h is kept the temperature, obtains humic 5% neopelex is added in sour charcoal-silica two-phase compound, and wet ball grinding is modified, obtains humic acid charcoal-two Silica dual phase filler.Using the method for melt blending, according to formula NS, zinc oxide, fatty acid, filler, sulphur, each ingredient Ratio (mass parts, phr) is 100:1:3:1:50:1.75, and humic acid carbon filling material and butadiene-styrene rubber are carried out melt blending, fourth is made Benzene glue composite material.Mechanical property is as shown in table 1.
1 humic acid charcoal of table-silica dual phase filler mechanical property of vulcanized rubber

Claims (2)

1. a kind of humic acid charcoal-silica two-phase compounded mix preparation method, it is characterised in that: the method includes as follows Step:
A, silica solution is added to the humic acid after drying, wherein the additional amount of silica solution is the 0% ~ 30% of humic acid quality, add water, It is handled by wet ball grinding, is dried to obtain humic acid-silica solution mixture；
B, by humic acid-silica solution mixture in N2Charing process is carried out under conditions of 800 ~ 1200 DEG C under atmosphere, obtains humic Sour charcoal-silica two-phase compound；
C, modifying agent is added to humic acid charcoal-silica two-phase compound, wet ball grinding is modified, obtains modified humic acid Charcoal-silica two-phase compounded mix product, wherein the additive amount of the modifying agent is that humic acid charcoal-silica two-phase is compound The 2% ~ 10% of packing quality.
2. preparation method according to claim 1, it is characterised in that: modifying agent described in step b is derived from silane coupling agent Silicon 69, Aluminate, titanate esters, hexa methyl silazane, neopelex, cetyl trimethylammonium bromide or poly- second two Any one in alcohol.
CN201810972101.3A 2018-08-24 2018-08-24 A kind of preparation method of humic acid charcoal-silica two-phase compounded mix Pending CN109054447A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1190977A (en) * 1995-05-22 1998-08-19 卡伯特公司 Elastomeric compounds incorporating silicon-treated carbon blacks
CN101210118A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Method for preparing carbon coating graphite/silicon oxide composite material
CN103937293A (en) * 2014-04-28 2014-07-23 北京化工大学 Carbon-coated white carbon black
CN106188624A (en) * 2016-07-20 2016-12-07 河南理工大学 A kind of preparation method of rice hull carbon silica core-shell two-phase compounded mix
CN106935823A (en) * 2017-03-20 2017-07-07 郑州大学 A kind of lithium ion battery negative material Sn/C and preparation method thereof
CN107603280A (en) * 2017-08-07 2018-01-19 湖州同泰新材料有限公司 A kind of preparation method of white carbon

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1190977A (en) * 1995-05-22 1998-08-19 卡伯特公司 Elastomeric compounds incorporating silicon-treated carbon blacks
CN101210118A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Method for preparing carbon coating graphite/silicon oxide composite material
CN103937293A (en) * 2014-04-28 2014-07-23 北京化工大学 Carbon-coated white carbon black
CN106188624A (en) * 2016-07-20 2016-12-07 河南理工大学 A kind of preparation method of rice hull carbon silica core-shell two-phase compounded mix
CN106935823A (en) * 2017-03-20 2017-07-07 郑州大学 A kind of lithium ion battery negative material Sn/C and preparation method thereof
CN107603280A (en) * 2017-08-07 2018-01-19 湖州同泰新材料有限公司 A kind of preparation method of white carbon

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