CN108832092A - Core-shell structure multi-element composite material, preparation method and the lithium ion battery comprising the multi-element composite material - Google Patents
Core-shell structure multi-element composite material, preparation method and the lithium ion battery comprising the multi-element composite material Download PDFInfo
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- CN108832092A CN108832092A CN201810594939.3A CN201810594939A CN108832092A CN 108832092 A CN108832092 A CN 108832092A CN 201810594939 A CN201810594939 A CN 201810594939A CN 108832092 A CN108832092 A CN 108832092A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention discloses a kind of core-shell structure multi-element composite material, preparation method and include the lithium ion battery of the multi-element composite material.The multi-element composite material includes graphite kernel and the shell for being coated on the core surface, and the shell includes chain hard carbon layer and soft carbon layer from inside to outside.The method includes：1) presoma of agraphitic carbon, solvent and surfactant are mixed, obtains the first presoma of liquid phase；2) inner nuclear material graphite and chain high molecular material are mixed, and carries out surface modification treatment, obtain the second presoma；3) the first presoma of the second presoma and liquid phase is used, is handled by cladding and compound third presoma is made, and be carbonized, obtain core-shell structure multi-element composite material.Method of the invention is simple, process is short, low in cost, environmentally friendly pollution-free, and obtained multi-element composite material possesses compacted density height, for the first time reversible capacity and the feature that coulombic efficiency is high for the first time, processing performance and cryogenic property are excellent.
Description
Technical field
The present invention relates to lithium ion battery negative material field, it is related to a kind of core-shell structure multi-element composite material, its preparation
Method and lithium ion battery comprising the multi-element composite material more particularly to a kind of core-shell structure multi-component composite anode material, its
Preparation method and lithium ion battery comprising the multi-component composite anode material.
Background technique
The application field of lithium ion battery expands to new-energy automobile field by 3C consumer electronics, and this requires lithiums
Ion battery has low cost, long circulating, excellent rate charge-discharge performance, reliable safety and excellent low temperature charge and discharge
Electrical property.The emphasis that the high rate performance and low temperature charge-discharge performance for how promoting lithium ion battery are always studied both at home and abroad.State
Inside and outside research report, the method that can be obviously improved graphite negative electrodes material mainly has surface modified, i.e., in Graphite Coating
Soft carbon or hard carbon, to achieve the purpose that improve material at low temperature performance.
If CN 102683646A discloses a kind of preparation method of composite cathode material for lithium ion cell, the invention is by stone
Ink is added in dispersing agent, and then hard carbon particle is also added in aqueous dispersion, then the two is mixed and carries out electrostatic spinning
Processing.Finally by electrostatic spinning product grinding, dry, carbonization.This method hard carbon particle and graphite matrix are still solid granulates
The physical bond of shape can not accomplish homogeneously to disperse, meanwhile, electrostatic spinning process is excessively complicated and with high costs, is unfavorable for big
Scale commercial metaplasia produces.CN 103151497A discloses a kind of preparation method of low-temperature lithium ion battery negative electrode material, the invention
By natural graphite with soft carbon mixed grinding, after 30-400 DEG C of carbonization treatment, add organic molten dissolved with polymer
Agent.Organic solvent pulps are stood later, be evaporated, are sieved, it is negative to prepare low temperature lithium battery by low-temperature setting and high temperature cabonization
Pole material.The material at low temperature better performances that this method obtains, but this method successively passes through heat treatment process for several times, produces
Journey is complicated and energy consumption is higher, and polymer precursor needs to be dissolved into organic solvent, and needs to be evaporated organic solvent, cost compared with
It is high and unfriendly to environment.
Therefore, a kind of simple process is researched and developed, the multi-component composite anode material that cryogenic property is excellent, cost of manufacture is cheap is
The technical problem in lithium ion battery negative material field.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of core-shell structure multi-element composite materials, its system
Preparation Method and lithium ion battery comprising the multi-element composite material, especially a kind of core-shell structure multi-component composite anode material, its
Preparation method and lithium ion battery comprising the multi-component composite anode material.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of core-shell structure multi-element composite material, the multi-element composite material includes graphite
Kernel and the shell for being coated on the core surface, the shell include chain hard carbon layer and soft carbon layer from inside to outside.
" chain hard carbon layer " of the present invention refers to：The clad is made of chain hard carbon, and " the soft carbon layer " refers to：The packet
The group of coating becomes soft carbon.
In core-shell structure multi-element composite material of the invention, graphite surface is the clad that chain hard carbon material is formed, then
Amorphous carbon layer is further coated, the composite material of Multi-layers distributing is formed, which is the homogeneous of covering material and core material
Dispersion, improves traditional physical bond, and compound coating layer is enabled to play covered effect more evenly.Meanwhile by hard carbon
Combine with the respective advantage of soft carbon, effectively improves the low temperature charge-discharge performance and high-temperature storage performance of material.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
Preferably, the median particle diameter of the multi-element composite material be 5 μm~45 μm, such as 5 μm, 7 μm, 8 μm, 10 μm,
12.5 μm, 18 μm, 22 μm, 26 μm, 30 μm, 35 μm, 40 μm, 42 μm or 45 μm etc., preferably 8 μm~25 μm, further preferably
It is 12 μm~22 μm.
Preferably, the specific surface area of the multi-element composite material is 1m2/ g~50m2/ g, such as 1m2/g、 5m2/g、8m2/
g、12m2/g、15m2/g、20m2/g、25m2/g、30m2/g、35m2/g、40m2/g、 45m2/ g or 50m2/ g etc., preferably
1.2m2/ g~3m2/g。
Preferably, the powder body compacted density of the multi-element composite material is 1g/cm3~2g/cm3, such as 1 g/cm3、
1.1g/cm3、1.2g/cm3、1.3g/cm3、1.5g/cm3、1.7g/cm3、1.8g/cm3Or 2g/cm3Deng preferably 1.1g/cm3~
1.7g/cm3。
It preferably, is the mass percent of the graphite kernel in terms of 100% by the gross mass of the multi-element composite material
It is 50%~99%, such as 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% etc..
It preferably, is the quality percentage of the chain hard carbon layer in terms of 100% by the gross mass of the multi-element composite material
Than be 0.01%~25%, such as 0.01%, 0.05%, 0.1%, 0.3%, 1%, 2%, 3%, 4%, 6%, 8%, 10%,
15%, 18%, 20%, 22%, 23% or 25% etc., preferably 1%~10%.
It preferably, is in terms of 100% by the gross mass of above-mentioned multi-element composite material, the mass percent of the soft carbon layer is
0.01%~25%, for example, 0.01%, 0.05%, 0.1%, 0.3%, 1%, 2%, 3%, 4%, 6%, 8%, 10%,
15%, 18% or 20% etc..
The mass percent of above-mentioned chain hard carbon layer and soft carbon layer preferably up to 1%~10% is advantageous in that respectively, not only
Compound coating layer can be improved in the uniform covered effect of core surface, can also preferably play the combination advantage of the two, more
The low temperature charge-discharge performance and high-temperature storage performance of material are promoted well.
Preferably, the graphite is natural Scaly graphite, natural cryptocrystal graphite, native crystal veiny graphite or artificial
Any a kind or at least two kinds of of combination in graphite.
Preferably, the shape of the graphite is sheet, graininess (can be the particle of rule, be also possible to irregular
Particle), any a kind or at least two kinds of of combination in spherical or spherical shape.
As the optimal technical scheme of multi-element composite material of the present invention, the chain hard carbon layer is by chain macromolecule
Compound is transformed through carbonization.
Preferably, the temperature of the carbonization is 600 DEG C~1300 DEG C, such as 600 DEG C, 650 DEG C, 700 DEG C, 800 DEG C, 900
DEG C, 1000 DEG C, 1100 DEG C, 1150 DEG C, 1200 DEG C or 1300 DEG C etc..
Preferably, the chain-like macromolecule compound is with branch or in not branched chain-like macromolecule compound
Any a kind or 2 kinds of combination.
Preferably, the chain-like macromolecule compound be thermoplastic, it is thermoplastic resin, natural fiber, artificial synthesized
Fiber, the fiber of chemical modification, natural rubber, asynthetic rubber, native cellulose, artificial synthetic fiber element, chemical modification
Cellulose, the cellulose ether of chemical modification, any a kind or at least two kinds of of combination in polyolefin or improved polyalkene, it is excellent
Be selected as native cellulose, artificial synthetic fiber element, the cellulose of chemical modification, the cellulose ether of chemical modification, natural rubber,
Any a kind or at least two kinds of of combination in asynthetic rubber, the rubber of chemical modification, polyolefin or improved polyalkene.
Polyolefin of the present invention can be the polyolefin of low-pressure polymerization preparation, be also possible to the poly- of high pressure polymerisation preparation
Alkene.
Preferably, the molecular weight of the chain-like macromolecule compound is 200 grams/mol~2000000 grams/mol, such as
200 grams/mol, 500 grams/mol, 1000 grams/mol, 2000 grams/mol, 5000 grams/mol, 10000 grams/mol, 50000
Gram/mol, 80000 grams/mol, 100000 grams/mol, 500000 grams/mol, gram/mol, 1000000 grams/mol,
1500000 grams/mol or 2000000 grams/mol etc., preferably 500 grams/mol~500000 grams/mol, further preferably
It is 1000 grams/mol~100000 grams/mol.
Preferably, the soft carbon layer is amorphous carbon layer, and the agraphitic carbon is conductive black, carbon fiber, organic matter heat
Crack any a kind or at least two kinds of of combination in carbon or plant pyrolytic carbon.
Second aspect, the present invention provide the preparation method of core-shell structure multi-element composite material as described in relation to the first aspect, institute
The method of stating includes the following steps：
(1) presoma of agraphitic carbon, solvent and surfactant are mixed, obtains the first presoma of liquid phase；
(2) inner nuclear material graphite and chain high molecular material are mixed, and carries out surface modification treatment, before obtaining second
Drive body；
(3) the first presoma of the second presoma and liquid phase is used, is handled by cladding and compound third presoma is made；
(4) it is carbonized to compound third presoma, obtains core-shell structure multi-element composite material.
In method of the invention, before step (1) realizes the modification to the presoma of agraphitic carbon and forms liquid phase first
Body is driven, forms the third presoma of multi-layer stable structure for use in subsequent cladding processing.
In method of the invention, chain high molecular material is coated to stone by the composite modified method of physics by step (2)
The surface of black kernel, in order to which subsequent cladding processing forms the third presoma of multi-layer stable structure.
In method of the invention, step (3) is handled by cladding, and cladding has gone up soft carbon layer on the surface of the material.
It, can be with final product nucleocapsid knot that collective effect makes by the design of above-mentioned operation and the cooperation of each step
Structure multi-element composite material stable structure, compacted density height, processing performance and cryogenic property are excellent.
Method processing technology of the invention is simple, low in cost, and obtained core-shell structure multi-element composite material has preferable
Low temperature charge-discharge characteristic.
As the optimal technical scheme of the method for the invention, the method also includes step is carried out after step (4)
(5)：Magnetic is broken up, sieved and removed to composite material after the carbonization obtained to step (4), obtains core-shell structure multiple elements design
Material.
Preferably, the presoma of step (1) described agraphitic carbon includes asphalt, coal tar pitch or carbonaceous mesophase spherules
(MCMB) any a kind or at least two kinds of of combination in.
Preferably, step (1) solvent is any a kind or at least two kinds of of combination in water, alcohol, ketone or ether.
The preferred distilled water of water of the present invention.
Preferably, step (1) surfactant is sodium tripolyphosphate, calgon, sodium pyrophosphate, triethyl group
Hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyglycol second two
Alcohol ester, cetyl trimethylammonium bromide, polyethylene glycol are to isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, poly-
Any a kind or at least two kinds of of combination in ethylene oxide Sorbitan Monooleate, p-ethylbenzoic acid or polyetherimide.
Preferably, mechanical stirring is also carried out after step (1) described mixing.
It preferably, is step (1) in terms of 100% by the gross mass of the presoma of agraphitic carbon, solvent and surfactant
The mass percent of the presoma of the agraphitic carbon, solvent and surfactant is respectively (20%~25%), 70% and
(5%~10%).
As the optimal technical scheme of the method for the invention, step (2) surface is modified modified using mechanical-physical
Any a kind in the modified method of method, gas chemistry or the modified method of liquid phase chemical.
Preferably, the modified method of the mechanical-physical includes the following steps：By inner nuclear material graphite and chain high molecular material
Mixing, which is placed in fusion machine, merges, and obtains the second presoma.
Preferably, the revolving speed of the fusion machine be 500r/min~3000r/min, such as 500r/min, 800r/min,
1000r/min, 1500r/min, 1800r/min, 2000r/min, 2500r/min or 3000 r/min etc..
Preferably, the fusion rounding machine cutter gap width be 0.01cm~0.5cm, such as 0.01cm, 0.05cm,
0.1cm, 0.2cm, 0.3cm, 0.4cm or 0.5cm etc..
Preferably, the time of fusion is at least 0.5h.
As the optimal technical scheme of the method for the invention, the processing of step (3) cladding using gas phase cladding,
Any a kind or at least two kinds of of combination in liquid phase coating method or solid phase cladding process.
Preferably, the liquid phase coating method includes the following steps：Second presoma is added to the first presoma of liquid phase
In, then dispersion carries out mist projection granulating under the protection of protective gas, obtains compound third presoma.
Preferably, in the liquid phase coating method, protective gas is in nitrogen, helium, neon, argon gas, Krypton or xenon
Any a kind or at least two kinds of of combination.
Preferably, in the liquid phase coating method, the revolving speed for the equipment that mist projection granulating uses is 5000r/min~25000r/
Min, for example, 5000r/min, 7500r/min, 10000r/min, 12000r/min, 15000r/min, 16500r/min,
18000r/min, 20000r/min or 25000r/min etc..
Preferably, in the liquid phase coating method, equipment inlet temperature that mist projection granulating uses is 25 DEG C~400 DEG C, example
Such as 25 DEG C, 50 DEG C, 85 DEG C, 100 DEG C, 120 DEG C, 155 DEG C, 185 DEG C, 200 DEG C, 235 DEG C, 260 DEG C, 300 DEG C, 325 DEG C, 350 DEG C
Or 400 DEG C etc., preferably 100 DEG C~300 DEG C.
Preferably, in the liquid phase coating method, equipment discharge port temperature that mist projection granulating uses for room temperature (15 DEG C)~
150 DEG C, such as 10 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 50 DEG C, 80 DEG C, 100 DEG C, 115 DEG C, 130 DEG C or 150 DEG C etc., preferably 60
DEG C~100 DEG C.
Preferably, in the liquid phase coating method, the feed rate for the slurry that mist projection granulating uses is 0.01 L/min~1L/
Min, such as 0.01L/min, 0.05L/min, 0.1L/min, 0.3L/min, 0.5L/min, 0.7L/min or 1L/min etc..
Preferably, in the liquid phase coating method, the solid content of the slurry that mist projection granulating uses is 10%~80%, preferably
It is 20%~60%, such as 20%, 25%, 30%, 40%, 45%, 50%, 55% or 60% etc..
Preferably, when cladding processing is using gas phase cladding, without step (4) after gas phase is covered to complete
Carburising step, the gas phase cladding includes the following steps：The powder body material that need to carry out gas phase cladding is placed in CVD deposition
In furnace, it is passed through carbon-source gas at 500 DEG C~1200 DEG C, gas phase cladding and carbonization are completed in CVD deposition furnace.
Preferably, in the gas phase cladding, carbon-source gas includes appointing in the gases such as methane, acetylene, ethylene or propylene
It anticipates a kind of or at least two mixed gas.
Preferably, in the gas phase cladding, CVD deposition furnace is rotary CVD deposition furnace, the rotary CVD deposition
The revolving speed of furnace is preferably 1r/min-50r/min, such as 1r/min, 5r/min, 10r/min, 15r/min, 20r/min, 25r/
Min, 30r/min, 40r/min or 50r/min etc..
Preferably, in the gas phase cladding, the reaction time is 2h~for 24 hours, for example, 2h, 5h, 8h, 10h, 13h, 15h,
16h, 18h, 20h, 22h or for 24 hours etc..
Preferably, the solid phase cladding process includes the following steps：It will need to carry out the powder body material and packet of solid phase cladding
It covers agent and is proportionally placed in mixing machine and mixed, be uniformly mixed material.
Preferably, in the solid phase cladding process, mixing machine includes mechanical fusion machine, VC batch mixer, Horizontal type mixer or spiral shell
Any one in belt batch mixer.
Preferably, in the solid phase cladding process, revolving speed when mixing is 10r/min~5000r/min, such as 10r/
min、50r/min、100r/min、200r/min、400r/min、800r/min、1200r/min、 1500r/min、2000r/
Min, 2500r/min, 3000r/min, 3500r/min, 4000r/min, 4500r/min or 5000r/min etc..
Preferably, the time of solid phase cladding is 0.1min~200min, for example, 0.1min, 1min, 5min,
15min, 30min, 45min, 60min, 80min, 100min, 120min, 150min, 180min or 200min etc..
As the optimal technical scheme of the method for the invention, step (4) carbonization includes the following steps：By step
(3) the compound third presoma of gained is placed in reactor, is passed through protective gas, is warming up to 600 DEG C~1300 DEG C, and heat preservation obtains
To core-shell structure multi-element composite material.
Preferably, during step (4) described carbonization, time of heat preservation is 0.5h~10h, for example, 0.5h, 1h, 2h,
3h, 5h, 6h, 8h or 10h etc..
Preferably, it during step (4) described carbonization, is cooled down after heat preservation.
Preferably, during step (4) described carbonization, reactor includes vacuum drying oven, batch-type furnace, rotary furnace, roller-way
Any a kind in furnace, pushed bat kiln or tube furnace.
Preferably, during step (4) described carbonization, protective gas is nitrogen, helium, neon, argon gas or xenon
In any a kind or at least two kinds of of combination.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) presoma of agraphitic carbon, solvent and surfactant are mixed, mechanical stirring obtains the first forerunner of liquid phase
Body；
(2) inner nuclear material graphite and chain high molecular material are mixed, is placed in fusion machine and merges at least 0.5h, obtains
To the second presoma；
(3) the second presoma is added in the first presoma of liquid phase, is uniformly dispersed by mechanical stirring, is then protected again
Mist projection granulating is carried out under the protection of shield property gas, obtains compound third presoma；
(4) compound third presoma is placed in reactor, is passed through protective gas, be warming up to 600 DEG C~1300 DEG C,
0.5h~10h is kept the temperature, the carbonization to compound third presoma is completed；
(5) magnetic is broken up, sieved and remove, core-shell structure multi-element composite material is obtained；
Wherein, the revolving speed of step (2) fusion machine is 500r/min~3000r/min, and fusion rounding machine cutter gap width is
0.01cm~0.5cm；
For 5000r/min~25000r/min, inlet temperature is the revolving speed for the equipment that step (3) mist projection granulating uses
100 DEG C~300 DEG C, discharge port temperature is 60 DEG C~100 DEG C；Mist projection granulating use solid content for 20%~60% slurry and
The feed rate of slurry is 0.01L/min~1L/min.
The third aspect, the present invention provide a kind of electrode material, and the electrode material is core-shell structure described in first aspect
Multi-element composite material.
Preferably, the electrode material is negative electrode material.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes electricity described in the third aspect
Pole material.
Compared with the prior art, the present invention has the advantages that：
(1) present invention employs the mode that surface recombination modified and coating modification technology combines, being successfully prepared has
The core-shell structure copolymer multi-element composite material of more structures is a kind of composite negative pole material haveing excellent performance.
Chain high molecular material is coated on graphite inner nuclear material surface by the composite modified method of physics by the present invention,
The soft carbon material being modified then is dissolved in the first presoma of liquid phase of solvent formation again and is coated with chain high molecular material
Material surface is coated soft carbon layer by coating technology by graphite, has obtained multi-element composite material eventually by carbonization.
(2) method of the invention is with process is simple, process is short, low in cost and environmentally friendly pollution-free
The advantages of.
(3) multi-element composite material of the invention possess compacted density it is high, for the first time reversible capacity and for the first time coulombic efficiency it is high,
Processing performance and the excellent feature of cryogenic property, are a kind of multi-component composite anode materials haveing excellent performance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of multi-component composite anode material in the embodiment of the present invention 1, wherein 1- graphite kernel, 21-
Chain hard carbon layer, 22- soft carbon layer, 2- shell；
Fig. 2 is the SEM figure of multi-component composite anode material in the embodiment of the present invention 1；
Fig. 3 is the XRD diagram of multi-component composite anode material in the embodiment of the present invention 1；
Fig. 4 is bent using the first charge-discharge of battery made of the multi-component composite anode material in the embodiment of the present invention 1
Line；
Fig. 5 is the cycle performance curve using battery made of the multi-component composite anode material in the embodiment of the present invention 1.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
It is tested using negative electrode material of the following methods to each embodiment and comparative example：
Negative electrode tab compacted density of the present invention=(cathode tablet quality-copper foil quality)/(negative electrode tab area × pole piece
Thickness after compacting).
Material is tested using the full-automatic specific surface area of the Tristar3000 of Micromeritics Instrument Corp. U.S.A and lacunarity analysis instrument
The specific surface area of material.
Using the average grain of 2000 test material particle size range of Malvern laser particle analyzer MS and feed particles
Diameter.
Using the structure of X-ray diffractometer X ' Pert Pro, PANalytical test material.
Using the surface microscopic topographic of Hitachi, Ltd's S4800 scanning electron microscope observation sample.
Electrochemistry cycle performance is tested using following methods：By mass percentage by negative electrode material, conductive agent and binder
95.5:1.5:3 dissolutions mix in a solvent, and control solid content is coated in copper foil current collector 50%, and vacuum drying is made
Cathode pole piece；Then the LiPF of the tertiary cathode pole piece, 1mol/L that prepared by traditional mature technology6/ EC+DMC+EMC (v/v=
1:1:1) electrolyte, Celgard2400 diaphragm, shell assemble 18650 cylinder single batteries using conventional production process.
The charge-discharge test of cylindrical battery is on Wuhan Jin Nuo Electronics Co., Ltd. LAND battery test system, in room temperature
Condition, 0.2C constant current charge-discharge, charging/discharging voltage are limited in 2.75~4.2V.
Embodiment 1
(1) by pitch, water and fatty acid polyethylene glycol ester according to 20:70:10 ratio is mixed, by mixture into
Row mechanical stirring is uniformly mixed and obtains asphalt emulsification dispersion liquid, i.e. the first presoma of liquid phase.
(2) by partial size be 5-20 μm artificial graphite, sodium carboxymethylcellulose is according to 70:30 ratio is mixed, will
Mixture is placed in fusion machine, and adjusting revolving speed is 1000 revs/min, and cutter gap width is 0.03 centimetre, and time of fusion is
0.5 hour, obtain the second presoma.
(3) the second presoma is added in the first presoma of liquid phase, carries out mechanical stirring, be uniformly mixed.By mixture
Presoma is placed in spray drying device, carries out mist projection granulating.Use during mist projection granulating nitrogen as protective gas,
Spray granulation equipment revolving speed is 18000 revs/min, and inlet temperature is set as 250 DEG C, and discharge port temperature is 100 DEG C, charging
Speed speed is 150mL/min.Compound third presoma is obtained by mist projection granulating.
(4) third presoma is placed in pushed bat kiln and carries out carbonization treatment.The maximum temperature of pushed bat kiln is set as 1150
DEG C, soaking time is 2 hours, uses nitrogen as protective gas.By cooled to room temperature, sample is by breaing up, sieving
Divide and remove magnetic, obtains the core-shell structure multi-component composite anode material that partial size is 5~40 μm.
Fig. 1 is the structural schematic diagram of multi-component composite anode material in the present embodiment, wherein 1- graphite kernel, 21- chain
Hard carbon layer, 22- soft carbon layer, 2- shell.
Fig. 2 is scanning electron microscope (SEM) picture of multi-component composite anode material in the present embodiment, has figure to can be seen that the material
Material is spheroid shape or irregular powder body material.
Fig. 3 is the XRD diagram of multi-component composite anode material in the present embodiment, and having figure to can be seen that material is graphite crystal structure
At the spectrogram of amorphous carbon is not fairly obvious.
Fig. 4 is bent using the first charge-discharge of battery made of the multi-component composite anode material in the embodiment of the present invention 1
Line, as seen from the figure, the capacity of the material are 353mAh/g, and charge and discharge platform is typical graphite material feature.
Fig. 5 is the cycle performance curve using battery made of the multi-component composite anode material in the embodiment of the present invention 1,
As seen from the figure, which possesses very good cyclical stability, and room temperature 1C/1C is recycled 1200 weeks, and capacity retention ratio is about
It is 90%.
Embodiment 2
By pitch, water and lauryl sodium sulfate according to 25:70:5 ratio is mixed, and mixture is carried out mechanical
Stirring is uniformly mixed and obtains asphalt emulsification dispersion liquid, i.e. the first presoma of liquid phase.
(2) by partial size be 5-20 μm natural spherical plumbago, sodium carboxymethylcellulose is according to 70:30 ratio is mixed
It closes, mixture is placed in fusion machine, adjusting revolving speed is 1000 revs/min, and cutter gap width is 0.03 centimetre, when fusion
Between be 0.5 hour, obtain the second presoma.
(3) the second presoma is added in the first presoma of liquid phase, carries out mechanical stirring, be uniformly mixed.By mixture
Presoma is placed in vacuum oven and is dried, temperature be 120 DEG C constant temperature drying 6 hours, vacuum degree be -0.1MPa.To water
It after dividing evaporation, is broken up with VC batch mixer, revolving speed is 1200 revs/min, and the time is 3 minutes, obtains compound third forerunner
Body.
(4) carbonization treatment will be carried out in compound third presoma Zhi Yu Bowl formula furnace, temperature is set as 1000 DEG C, and constant temperature 2 is small
When, it the use of nitrogen is protective gas.After heating, through cooled to room temperature, sample is obtained by breaing up, sieving and except magnetic
The multi-component composite anode material for being 5~40 μm to partial size.
Embodiment 3
(1) by coal tar, water and polyvinylpyrrolidone according to 23:70:7 ratio is mixed, and mixture is carried out
Mechanical stirring is uniformly mixed and obtains the first presoma of liquid phase.
(2) by natural Scaly graphite, natural rubber according to 70:30 ratio is mixed, and mixture is placed in fusion machine
In, adjusting revolving speed is 2000 revs/min, and cutter gap width is 0.15 centimetre, and time of fusion is 3 hours, obtains the second forerunner
Body.
(3) the second presoma is added in the first presoma of liquid phase, carries out mechanical stirring, be uniformly mixed.By mixture
Presoma is placed in spray drying device, carries out mist projection granulating.Use during mist projection granulating nitrogen as protective gas,
Spray granulation equipment revolving speed is 10000 revs/min, and inlet temperature is set as 200 DEG C, and discharge port temperature is 80 DEG C, charging speed
Degree speed is 500mL/min.Compound third presoma is obtained by mist projection granulating.
(4) third presoma is placed in pushed bat kiln and carries out carbonization treatment.The maximum temperature of pushed bat kiln is set as 950 DEG C,
Soaking time is 10 hours, uses helium as protective gas.By cooled to room temperature, sample is by breaing up, sieving
And magnetic is removed, obtain core-shell structure multi-component composite anode material.
Embodiment 4
By sucrose, ethyl alcohol and polyoxyethylene sorbitan monooleate according to 24:70:6 ratio is mixed, will
Mixture carries out mechanical stirring, is uniformly mixed and obtains the first presoma of liquid phase.
(2) by native crystal veiny graphite, chemical modification cellulose ether according to 70:30 ratio is mixed, and will be mixed
It closes object to be placed in fusion machine, adjusting revolving speed is 2500 revs/min, and cutter gap width is 0.4 centimetre, and time of fusion is 6 small
When, obtain the second presoma.
(3) the second presoma is added in the first presoma of liquid phase, carries out mechanical stirring, be uniformly mixed.By mixture
Presoma is placed in vacuum oven and is dried, temperature be 135 DEG C constant temperature drying 4 hours, vacuum degree be -0.1MPa.To water
It after dividing evaporation, is broken up with VC batch mixer, revolving speed is 1500 revs/min, and the time is 10 minutes, obtains compound third forerunner
Body.
(4) compound third presoma is placed in tube furnace and carries out carbonization treatment, temperature is set as 1200 DEG C, constant temperature 6.5
Hour, it the use of nitrogen is protective gas.After heating, through cooled to room temperature, sample, which passes through, breaks up, sieves and removes magnetic,
Obtain multi-component composite anode material.
Embodiment 5
Except adjustment fusion machine revolving speed is 650r/min, fusion rounding machine cutter gap width is 0.5cm, time of fusion 12h；
Carbonization Conditions are：800 DEG C of heat preservation 10h；The equipment revolving speed that mist projection granulating uses is 8000r/min, and 220 DEG C of inlet temperature, out
Except 100 DEG C of material mouth temperature, other content is same as Example 1
Embodiment 6
(1) by pitch, water and lauryl sodium sulfate according to 25:70:5 ratio is mixed, and mixture is carried out machine
Tool stirring, is uniformly mixed and obtains asphalt emulsification dispersion liquid, i.e. the first presoma of liquid phase.
(2) natural spherical plumbago that partial size is 5-20 μm is added in the first presoma, after being sufficiently stirred 20 minutes,
Then mixture is placed in vacuum oven and is dried, temperature be 120 DEG C constant temperature drying 6 hours, vacuum degree be-
0.1MPa.It after moisture evaporation, is broken up with VC batch mixer, revolving speed is 1200 revs/min, and the time is 3 minutes, is answered
Close the second presoma.
(3) the second presoma is placed in CVD deposition furnace, is passed through acetylene gas at 900 DEG C, in rotary CVD furnace
Complete gas phase cladding and carbonization.Reaction time is 12 hours, and rotary CVD furnace revolving speed is 6 revs/min.
(4) after heating, through cooled to room temperature, sample by breaing up, sieving and except magnetic, obtain partial size be 5~
40 μm of multi-component composite anode material.
Comparative example 1
Multi-component composite anode material is prepared according to method substantially the same manner as Example 1, difference is：Do not prepare first
Presoma directly mixes agraphitic carbon presoma, solvent, artificial graphite and high molecular material, after carrying out mist projection granulating
Carbonization.
The Electrochemical results of negative electrode material prepared by embodiment 1-6 and comparative example 1 are as shown in table 1.
Table 1
The negative electrode material prepared it can be seen from data in above table according to each embodiment the method is reversible for the first time
Capacity, for the first time coulombic efficiency, circulation volume conservation rate etc. chemical property are superior to the preparation of 1 the method for comparative example
Negative electrode material.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of core-shell structure multi-element composite material, which is characterized in that the multi-element composite material includes graphite kernel and packet
The shell of the core surface is overlayed on, the shell includes chain hard carbon layer and soft carbon layer from inside to outside.
2. multi-element composite material according to claim 1, which is characterized in that the median particle diameter of the multi-element composite material is
5 μm~45 μm, preferably 8 μm~25 μm, further preferably 12 μm~22 μm；
Preferably, the specific surface area of the multi-element composite material is 1m2/ g~50m2/ g, preferably 1.2m2/ g~3m2/g；
Preferably, the powder body compacted density of the multi-element composite material is 1g/cm3~2g/cm3, preferably 1.1g/cm3~
1.7g/cm3；
It preferably, is in terms of 100% by the gross mass of the multi-element composite material, the mass percent of the graphite kernel is 50%
~99%；
It preferably, is in terms of 100% by the gross mass of the multi-element composite material, the mass percent of the chain hard carbon layer is
0.01%~25%, preferably 1%~10%；
It preferably, is in terms of 100% by the gross mass of above-mentioned multi-element composite material, the mass percent of the soft carbon layer is 0.01%
~25%, preferably 1%~10%；
Preferably, the graphite is in natural Scaly graphite, natural cryptocrystal graphite, native crystal veiny graphite or artificial graphite
Any a kind or at least two kinds of of combination；
Preferably, the shape of the graphite is sheet, graininess, any a kind or at least two kinds of of group in spherical or spherical shape
It closes；
Preferably, the chain hard carbon layer is transformed by chain-like macromolecule compound through carbonization；
Preferably, the temperature of the carbonization is 600 DEG C~1300 DEG C；
Preferably, the chain-like macromolecule compound is any with branch or in not branched chain-like macromolecule compound
1 kind or 2 kinds of combination；
Preferably, the chain-like macromolecule compound be thermoplastic, thermoplastic resin, natural fiber, artificial synthetic fiber,
The fiber of chemical modification, natural rubber, asynthetic rubber, native cellulose, artificial synthetic fiber element, chemical modification fiber
Any a kind or at least two kinds of of combination in element, the cellulose ether of chemical modification, polyolefin or improved polyalkene, preferably naturally
Cellulose, artificial synthetic fiber element, the cellulose of chemical modification, the cellulose ether of chemical modification, natural rubber, artificial synthesized rubber
Any a kind or at least two kinds of of combination in glue, the rubber of chemical modification, polyolefin or improved polyalkene；
Preferably, the molecular weight of the chain-like macromolecule compound be 200 grams/mol~2000000 grams/mol, preferably 500
Gram/mol~500000 grams/mol, further preferably 1000 grams/mol~100000 grams/mol；
Preferably, the soft carbon layer is amorphous carbon layer, and the agraphitic carbon is conductive black, carbon fiber, organic matter thermal cracking
Any a kind or at least two kinds of of combination in carbon or plant pyrolytic carbon.
3. the preparation method of core-shell structure multi-element composite material as claimed in claim 1 or 2, which is characterized in that the method
Include the following steps：
(1) presoma of agraphitic carbon, solvent and surfactant are mixed, obtains the first presoma of liquid phase；
(2) inner nuclear material graphite and chain high molecular material are mixed, and carries out surface modification treatment, obtain the second presoma；
(3) the first presoma of the second presoma and liquid phase is used, is handled by cladding and compound third presoma is made；
(4) it is carbonized to compound third presoma, obtains core-shell structure multi-element composite material；
Preferably, the method also includes carrying out step (5) after step (4)：It is compound after the carbonization obtained to step (4)
Magnetic is broken up, sieved and removed to material, obtains core-shell structure multi-element composite material.
4. according to the method in claim 2 or 3, which is characterized in that the presoma of step (1) described agraphitic carbon includes stone
Any a kind or at least two kinds of of combination in oil asphalt, coal tar pitch or carbonaceous mesophase spherules MCMB；
Preferably, step (1) solvent is any a kind or at least two kinds of of combination in water, alcohol, ketone or ether；
Preferably, step (1) surfactant is sodium tripolyphosphate, calgon, sodium pyrophosphate, triethyl group hexyl phosphorus
Acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, ten
Six alkyl trimethyl ammonium bromides, polyethylene glycol are de- to isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene
Any a kind or at least two kinds of of combination in water sorbitol monooleate, p-ethylbenzoic acid or polyetherimide；
Preferably, mechanical stirring is also carried out after step (1) described mixing；
It preferably, is step (1) described nothing in terms of 100% by the gross mass of the presoma of agraphitic carbon, solvent and surfactant
Be formed the presoma of carbon, solvent and surfactant mass percent be respectively (20%~25%), 70% and (5%~
10%).
5. the method according to claim 3 or 4, which is characterized in that step (2) the surface modification is changed using mechanical-physical
Property method, the modified method of gas chemistry or the modified method of liquid phase chemical in any a kind；
Preferably, the modified method of the mechanical-physical includes the following steps：Inner nuclear material graphite and chain high molecular material are mixed
It is placed in fusion machine and merges, obtain the second presoma；
Preferably, the revolving speed of the fusion machine is 500r/min~3000r/min；
Preferably, the fusion rounding machine cutter gap width is 0.01cm~0.5cm；
Preferably, the time of fusion is at least 0.5h.
6. according to the described in any item methods of claim 3-5, which is characterized in that step (3) the cladding processing uses gas phase
Any a kind or at least two kinds of of combination in cladding process, liquid phase coating method or solid phase cladding process；
Preferably, the liquid phase coating method includes the following steps：Second presoma is added in the first presoma of liquid phase, point
It dissipates, mist projection granulating is then carried out under the protection of protective gas, obtains compound third presoma；
Preferably, in the liquid phase coating method, protective gas is appointing in nitrogen, helium, neon, argon gas, Krypton or xenon
The combination of a kind or at least two kinds of of meaning；
Preferably, in the liquid phase coating method, the revolving speed for the equipment that mist projection granulating uses is 5000r/min~25000r/min；
Preferably, in the liquid phase coating method, the equipment inlet temperature that mist projection granulating uses is 25 DEG C~400 DEG C, preferably
100 DEG C~300 DEG C；
Preferably, in the liquid phase coating method, the equipment discharge port temperature that mist projection granulating uses is 15 DEG C~150 DEG C, preferably
60 DEG C~100 DEG C；
Preferably, in the liquid phase coating method, the feed rate for the slurry that mist projection granulating uses is 0.01L/min~1L/min；
Preferably, in the liquid phase coating method, the solid content of the slurry that mist projection granulating uses is 10%~80%, preferably 20%
~60%；
Preferably, the carbonization when cladding processing is using gas phase cladding, after gas phase is covered to complete without step (4)
Step, the gas phase cladding include the following steps：The powder body material that need to carry out gas phase cladding is placed in CVD deposition furnace,
It is passed through carbon-source gas at 500 DEG C~1200 DEG C, gas phase cladding and carbonization are completed in CVD deposition furnace；
Preferably, in the gas phase cladding, carbon-source gas includes any one in methane, acetylene, ethylene or propylene gas
Or at least two mixed gas；
Preferably, in the gas phase cladding, CVD deposition furnace is rotary CVD deposition furnace, the rotary CVD deposition furnace
Revolving speed is preferably 1r/min-50r/min；
Preferably, in the gas phase cladding, the reaction time is 2h~for 24 hours；
Preferably, the solid phase cladding process includes the following steps：It will need to carry out the powder body material and covering of solid phase cladding
It is proportionally placed in mixing machine and is mixed, be uniformly mixed material；
Preferably, in the solid phase cladding process, mixing machine includes mechanical fusion machine, VC batch mixer, Horizontal type mixer or helical-ribbon type
Any one in batch mixer；
Preferably, in the solid phase cladding process, revolving speed when mixing is 10r/min~5000r/min；
Preferably, the time of the solid phase cladding is 0.1min~200min.
7. according to the described in any item methods of claim 3-6, which is characterized in that step (4) carbonization includes the following steps：
Compound third presoma obtained by step (3) is placed in reactor, protective gas is passed through, is warming up to 600 DEG C~1300 DEG C, is protected
Temperature obtains core-shell structure multi-element composite material；
Preferably, during step (4) described carbonization, the time of heat preservation is 0.5h~10h；
Preferably, it during step (4) described carbonization, is cooled down after heat preservation；
Preferably, during step (4) described carbonization, reactor includes vacuum drying oven, batch-type furnace, rotary furnace, roller furnace, push plate
Any a kind in kiln or tube furnace；
Preferably, during step (4) described carbonization, protective gas is in nitrogen, helium, neon, argon gas or xenon
Any a kind or at least two kinds of of combination.
8. according to the described in any item methods of claim 3-7, which is characterized in that the described method comprises the following steps：
(1) presoma of agraphitic carbon, solvent and surfactant are mixed, mechanical stirring obtains the first presoma of liquid phase；
(2) inner nuclear material graphite and chain high molecular material are mixed, is placed in fusion machine and merges at least 0.5h, obtains second
Presoma；
(3) the second presoma is added in the first presoma of liquid phase, is uniformly dispersed by mechanical stirring, then protectiveness gas again
Mist projection granulating is carried out under the protection of body, obtains compound third presoma；
(4) compound third presoma is placed in reactor, is passed through protective gas, be warming up to 600 DEG C~1300 DEG C, heat preservation
0.5h~10h completes the carbonization to compound third presoma；
(5) magnetic is broken up, sieved and remove, core-shell structure multi-element composite material is obtained；
Wherein, the revolving speed of step (2) fusion machine is 500r/min~3000r/min, and fusion rounding machine cutter gap width is 0.01cm
~0.5cm；
For the revolving speed for the equipment that step (3) mist projection granulating uses for 5000r/min~25000r/min, inlet temperature is 100 DEG C
~300 DEG C, discharge port temperature is 60 DEG C~100 DEG C；Mist projection granulating uses slurry and slurry of the solid content for 20%~60%
Feed rate is 0.01L/min~1L/min.
9. a kind of electrode material, which is characterized in that the electrode material is that core-shell structure of any of claims 1 or 2 is polynary multiple
Condensation material；
Preferably, the electrode material is negative electrode material.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes electrode material as claimed in claim 9.
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| CN111987293A (en) * | 2019-05-21 | 2020-11-24 | 中国科学院物理研究所 | Nitric acid and/or nitrate modified carbon-based negative electrode material and preparation method and application thereof |
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Application publication date: 20181116 |