CN104638252B - Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery - Google Patents
Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery Download PDFInfo
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Abstract
The invention relates to a silicon composited negative electrode material, a preparation method of the silicon composited negative electrode material and a lithium ion battery adopting the silicon composited negative electrode material. The silicon composited negative electrode material is of a core-shell structure, the inner core is composed of graphite and a carbon nano tube coated on the surface of the graphite and filled with nanometer silicon, and the shell is a conductive carbon material cladding layer. According to the silicon composited negative electrode material, the high-pressure filling technology is adopted to enable nanometer silicon particles to be filled into the carbon nano tube, and therefore, the dispersibility and the electrical conductivity of the silicon particles are improved; and besides, the surface modification and homogeneous phase wrapping technology is combined to prepare the core-shell silicon composited negative electrode material successfully. According to the preparation method of the silicon composited negative electrode material, silicon, carbon and graphite are composited, silicon expansion and pulverization are inhibited, the cycle performance and the initial efficiency of the material are greatly promoted, and the prepared silicon composited negative electrode material has high compaction density and good processability, is environment-friendly and has no pollution.
Description
Technical field
The invention belongs to lithium ion battery negative material field, more particularly to a kind of silicon composite cathode material and its preparation side
Method, and using the lithium ion battery of the negative material.
Background technology
Lithium ion battery due to specific energy it is big, running voltage is high, service life cycle length, memory-less effect, put certainly
The advantages of electricity little, pollution free green environment protection, during portable mobile electronic equipment and electric automobile have been widely used in.At present, business
The lithium ion battery of industry mainly adopts graphite negative electrodes material, but its theoretical specific capacity is only 372mAh/g, it is impossible to meet
Demand of the following lithium ion battery to high-energy-density.Both at home and abroad research report, can form metallic element, the gold of alloy with lithium
Category oxide and metal alloy compound, such as Si, Sn, Ge, Sb, Pb, SiO, SnO, SbSn, Mg2Si etc., with higher specific volume
Amount.However, these materials in use battery capacity decay is very fast so as to practical application is subject to certain restrictions.
Think that metal simple-substance, alloy and the volumetric expansion of metal-oxide negative material removal lithium embedded contraction is larger and cause material
Material destruction and crushing, are to cause material capacity decay main cause faster.Therefore, suppress the volumetric expansion of material, improve material
The Stability Analysis of Structures of material is significant with metal-oxide negative material cyclical stability for alloy is improved.It is main by receiving at present
Meter Hua, alloying and with multiple elements design (compound with activity or non-active material) improving the volumetric expansion of material.
As CN 101521273A disclose one kind prepare stannum-carbon/core-shell structure copolymer nanoparticle filled carbon nano-tube be combined
The in-situ synthetic method of negative material, the invention cracks growth CNT using organic gas outside nanoparticle, by nanometer
Silicon particle is filled in CNT caliber, and the method resulting materials have higher capacity, and cycle performance is good, but the method
The growth of middle CNT is difficult to control to, loading than relatively low, and merely with the CNT conduct filled with active substance
Ion cathode material lithium is relatively costly, is unfavorable for commercialization.
CN 103199223A disclose a kind of Cu-Cr-Si ternarys negative material and preparation method thereof, the invention by copper powder,
Chromium powder, silica flour mixed calcining process prepare alloy ingot, subsequently crush, and obtain the Cu-Cr-Si ternarys with micron order size and close
Bronze body, resulting materials have the continuous phase size that silicon is formed with chromium in higher capacity, but the ternary material of the method preparation
Still it is larger, copper, chromium and silicon are not uniformly disperseed, cause material expand larger, cycle performance is poor.
CN 103560249A disclose a kind of multi-component composite anode material and preparation method, and the invention is by silica flour, carbon nanometer
Pipe, expanded graphite are added in polyvinyl alcohol or Polyethylene Glycol aqueous systems, then stir dry doubling and are burnt till, and are obtained by nano-silicon
The multi-element composite material of powder, CNT, expanded graphite and amorphous carbon composition, the conductivity of composite material is good, and capacity is high, but
In the method preparation process, it is difficult to sufficiently disperse nano silica fume, so as to cause the first charge-discharge efficiency of the material relatively low.
Therefore, the multiple elements design of a kind of high conductivity, high power capacity, high first charge-discharge efficiency and good cycling stability is researched and developed
Negative material is the technical barrier of field of lithium ion battery.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of silicon composite cathode material.The present invention
The negative material of offer has the advantages that good conductivity, capacity are high, first coulombic efficiency height, cycle performance are excellent.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of silicon composite cathode material, the negative material be nucleocapsid structure, kernel by graphite be coated in graphite surface
Silico-carbo nanotube complex constitute, shell be conductive carbon material clad.Fig. 1 is the silicon composite cathode material of the present invention
Structural representation.
Preferably, the silicon in the silico-carbo nanotube complex is filled in CNT footpath and its surface.It is described
Silicon in silico-carbo nanotube complex can be most of, and such as more than 50% is filled in CNT footpath, small part, for example
Less than 50% is attached to carbon nano tube surface.Above-mentioned filling mode is remarkably improved the electric conductivity of material, while can reduce
Dilation effect of the silicon materials in charge and discharge process.
Preferably, silicon is nano-silicon in the silicon composite cathode material, and median particle diameter is 10.0～150.0nm, preferably
20.0～100.0nm, more preferably 10.0～60.0nm；
Preferably, the siliceous 1～20wt% of the silicon composite cathode material, CNT 5～40%, graphite 30～
90wt%, conductive carbon material 4-50wt%.
Preferably, the median particle diameter of the silicon composite cathode material is 5.0～45.0 μm, preferably 8.0～35.0 μm,
More preferably 10.0～25.0 μm.
Preferably, the specific surface area of the silicon composite cathode material is 1.0～20.0m2/ g, preferably 1.5～8.0m2/g。
Preferably, the powder body compacted density of the silicon composite cathode material is 1.0～2.0g/cm3, preferably 1.1～
1.7g/cm3。
Preferably, the graphite is natural Scaly graphite, natural cryptocrystal graphite, native crystal veiny graphite, artificial
The combination of a kind or at least 2 kinds of graphite or electrically conductive graphite.
Preferably, the combination for being shaped as lamellar, spherical block or spherical a kind or at least 2 kinds of the graphite.
Preferably, the median particle diameter of the graphite be 5.0～30.0 μm, preferably 8.0～25.0 μm, more preferably
10.0～20.0 μm.
The second object of the present invention is to provide a kind of preparation method of silicon composite cathode material of the present invention, wherein
Silico-carbo nanotube complex is prepared using high pressure completion method is compound.The present invention carries out compound being capable of achieving using high pressure filling technique
Compound, and the modified multiple elements design that silicon, carbon and graphite are successfully realized with homogeneous coating technology of mating surface of silicon and CNT.
Preferably, the method comprising the steps of：
(1) nano-silicon is combined with CNT using high pressure completion method, obtains the first presoma；
(2) first presoma is coated in into graphite surface, obtains the second presoma；
(3) second presoma is carried out into coating modification, is sintered, obtain silicon composite cathode material.
Used as preferential, step is carried out after (3)：The composite negative pole material that step (4) obtains step (3) is crushed, sieved simultaneously
Except magnetic, the silicon composite cathode material that median particle diameter is 5.0～45.0 μm is obtained.
Preferably, the high pressure completion method prepares nano-silicon composite carbon nanotube comprising the following steps：CNT is pre-
Process, carbon nano-tube filled, high temperature reduction.
Preferably, the CNT pre-treatment step is：Under room temperature, by CNT be added to equipped with concentrated nitric acid/
In the flask of concentrated sulphuric acid mixed liquor, being subsequently placed in ultrasonic cleaner carries out 6～12h of ultrasonic oxidation, finally carries out sucking filtration, does
It is dry to obtain pure, port openings and defective oxide/carbon nanometer tube.
Preferably, described CNT is the mixing of a kind or at least 2 kinds in single-walled pipe, double-wall pipe, multi-walled pipes.
Preferably, the average caliber of the CNT is 40～200nm.
Preferably, the concentrated nitric acid and concentrated sulfuric acid volume ratio are 1～3:1.
Preferably, the carbon nano-tube filled step is：CNT after oxidation, nano-silicon, dispersant are added
To in organic solvent, after mixing, in being injected into high-pressure bottle, and noble gases, plus bulk container are passed through thereto, keep 1
～48 hours, last sucking filtration was dried to obtain black solid, is ground to powder, obtained the CNT of nano-silicon filling.
Preferably, the median particle diameter of described nano-silicon is 10.0～150.0nm, preferably 20.0～100.0nm, enters one
Step is preferably 10.0～60.0nm.
Preferably, the dispersant be sodium tripolyphosphate, sodium hexameta phosphate, sodium pyrophosphate, triethyl group hexyl phosphoric acid, 12
Alkyl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, cetyl
Trimethylammonium bromide, Polyethylene Glycol are to isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, Polyoxyethylene sorbitan
1 kind or at least 2 kinds of combination in alcohol monoleate, p-ethylbenzoic acid and Polyetherimide；
Preferably, the organic solvent is the combination of a kind or at least 2 kinds in alcohol, ketone and ether.
Preferably, the noble gases are the group of a kind or at least 2 kinds in nitrogen, helium, neon, argon and xenon
Close.
Preferably, after the oxidation CNT, nano-silicon, the mass concentration of dispersant be respectively 5～40%, 1～
20%th, 0.1～1.0% (preferably 0.5%).
Preferably, the mixing is carried out by stirring, preferably mixes 1～12h.
Preferably, pressure is to 1.0 × 10 plus in bulk container5～6.0 × 106Pascal.
Preferably, the time of the grinding is 0.5h～4h.
Preferably, the CNT high temperature reduction step is：The CNT that nano-silicon is filled is put into into heating anti-
In answering device, under atmosphere of inert gases protection, thermal reduction process is carried out, after cooling, obtain the reduction carbon nanometer of nano-silicon filling
Pipe.
Preferentially, the heating response device is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln or tube furnace.
Preferably, the noble gases are the group of a kind or at least 2 kinds in nitrogen, helium, neon, argon and xenon
Close, preferred gas flow is 0.1～5L/min.
Preferably, the temperature of the thermal reduction is 600 DEG C～1000 DEG C, and the time of thermal reduction is 10～120min.
Preferably, the heating rate during thermal reduction is 0.5～20.0 DEG C/min.
Preferably, step (2) coating is using mechanical-physical coating or liquid phase coating.Mechanical-physical coating or
Liquid phase coating can be completed using new technique known in the art or future.The present invention can be carried out using following method.
The mechanical-physical coating step is：Graphite and the presoma of the step (1) first are placed in fusion machine and are merged,
Obtain step (2) second presoma.
Preferably, the graphite is natural Scaly graphite, natural cryptocrystal graphite, native crystal veiny graphite, artificial stone
The combination of a kind or at least 2 kinds of black or electrically conductive graphite.
Preferably, the combination for being shaped as lamellar, spherical block or spherical a kind or at least 2 kinds of the graphite.
Preferably, the graphite median particle diameter be 5.0～30.0 μm, preferably 8.0～25.0 μm, more preferably
10.0～20.0 μm.
Preferably, the rotating speed of the fusion machine is 500.0～3000.0r/min.
Preferably, the fusion rounding machine cutter gap width is 0.01～0.5cm.
Preferably, the time of fusion is at least 0.5h.
The liquid phase coating step is：By step (1) first presoma and graphite in organic solvent system, spraying
It is dried, obtains the presoma of the step (2) second.
Preferably, the organic solvent is the combination of a kind or at least 2 kinds in ether, alcohol and ketone.
Preferably, step (3) coating modification is modified using gas phase coating modification, liquid phase coating or solid phase cladding changes
Property.The gas phase coating modification, liquid phase coating are modified or solid phase coating modification can adopt new skill known in the art or future
Art is completed.The present invention can be carried out using following method.
The gas phase coating modification step is：Step (2) second presoma is placed in rotary furnace, protectiveness is passed through
Gas, is warming up to 600～1200 DEG C, is passed through organic carbon source gas, and after 0.5～10.0h of insulation room temperature is cooled to, and obtains step
(3) silicon composite cathode material.
Preferably, the protective gas is a kind or at least 2 kinds in nitrogen, helium, neon, argon, Krypton and xenon
Combination.
Preferably, the organic carbon source gas is a kind in the arene derivant of hydro carbons and/or 1～3 ring or extremely
Few 2 kinds combination；1 kind preferably in methane, ethylene, acetylene, benzene,toluene,xylene, styrene and phenol or at least 2 kinds
Combination.
Preferably, the speed of gyration of the rotary furnace is 0.1～5.0r/min.
Preferably, the flow for being passed through organic carbon source gas is 0.1～2.0L/min.
The liquid phase coating modification procedure is：Step (2) second presoma and Organic substance are dispersed in into organic solvent
In system, it is spray-dried, in being subsequently placed in reactor, is passed through protective gas, is warming up to 600.0～1200.0 DEG C, insulation 0.5
Room temperature is cooled to after～10.0h, the step (3) silicon composite cathode material is obtained.
Preferably, the organic solvent is the combination of a kind or at least 2 kinds in ether, alcohol and ketone.
The solid phase coating modification step is：Step (2) second presoma and Organic substance are placed in VC mixers
Mixing, in being subsequently placed in reactor, is passed through protective gas, is warming up to 600.0～1200.0 DEG C, is incubated cold after 0.5～10.0h
But to room temperature, step (3) silicon composite cathode material is obtained.
Preferably, the rotating speed of the VC mixers is 500.0～3000.0r/min.
Preferably, described incorporation time is at least 0.5h.
Preferably, the protective gas is the group of a kind or at least 2 kinds in nitrogen, helium, neon, argon and xenon
Close.
Preferably, the modified reactor of the rotary furnace of the gas phase coating modification, liquid phase coating, solid phase coating modification it is anti-
The heating rate for answering device is 0.5～20.0 DEG C/min.
Preferably, the reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln or tube furnace.
Preferably, the Organic substance is a kind or at least 2 in polymer, saccharide, organic acid, Colophonium and macromolecular material
The combination planted, preferably epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polrvinyl chloride, poly- second two
1 kind or at least 2 kinds of combination in alcohol, poly(ethylene oxide), Kynoar, acrylic resin and polyacrylonitrile.
Preferably, the liquid phase coating and Organic substance in solid phase cladding are powder, and median particle diameter is 0.1～25.0 μm,
Particularly preferably 0.5～8.0 μm.
Sintering in step (3) can be carried out using method of the prior art.
The third object of the present invention is to provide a kind of lithium ion battery, and it includes silicon composite cathode material of the present invention
Material or silicon composite cathode material obtained in silicon composite cathode material preparation method of the present invention.
The fourth object of the present invention is to provide a kind of preparation method of lithium ion battery of the present invention, wherein negative pole pole
Piece is by the way that silicon composite cathode material of the present invention or silicon obtained in silicon composite cathode material preparation method of the present invention are answered
Close negative material, conductive agent and binding agent by mass percentage (91～94):(1～3):(3～6) dissolving in a solvent mixing,
Be coated in copper foil current collector, vacuum drying, be obtained.Then, by traditional maturation process prepare anode pole piece, electrolyte, every
Film, shell assemble lithium ion battery using conventional production process.
Preferably, the conductive agent is graphite powder and/or nano conductive liquid.
Preferably, the nano conductive liquid is made up of the nano-carbon material of 0.5-20wt% with dispersion solvent.
Preferably, the nano-carbon material is Graphene, CNT, carbon nano-fiber, fullerene, white carbon black and acetylene black
In a kind or at least 2 kinds of combination.
Preferably, the graphite flake number of plies of the Graphene is 1-100.
Preferably, a diameter of 0.2-500nm of the CNT or carbon nano-fiber.
Preferably, the particle diameter of the fullerene, white carbon black or acetylene black is 1-200nm.
Preferably, the binding agent is polyimide resin, acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, carboxylic first
The combination of a kind or at least 2 kinds of base sodium cellulosate or butadiene-styrene rubber.
Preferably, the solvent is a kind in N-Methyl pyrrolidone, dimethylformamide, acetone or methyl ethyl ketone
Or at least 2 kinds of combination.
Ternary material, rich lithium material of the adoptable positive electrode active materials of heretofore described anode pole piece for commercial type
The combination of a kind or at least 2 kinds of material, cobalt acid lithium, lithium nickelate, spinel lithium manganate, layer dress LiMn2O4 or LiFePO4；The lithium from
Sub- battery variety is conventional aluminum hull, box hat or soft bag lithium ionic cell.
The present invention using high-pressure process filling carbon nano-pipe technology, it is surface recombination modified in combination with coating modification by the way of into
Work(is prepared for nucleocapsid structure silicon composite cathode material.Realized using high pressure filling technique and silicon nanoparticle is inserted into carbon
In nanometer caliber, so as to lift the dispersibility and electric conductivity of silicon grain, the expansion for suppressing silicon greatly promotes material circulation performance；Separately
Outward, mating surface is composite modified is successfully prepared with core-shell structure copolymer silicon composite cathode material with coating modification technology, realizes silicon, carbon
And graphite multiple elements design, further lift material circulation performance (400 circulation volume conservation rates are more than 92%) and imitate first
Rate (>90%).Well, environmental friendliness is pollution-free for silicon composite cathode material compacted density height, the processing characteristics that the present invention is provided.
Description of the drawings
Fig. 1 is the structural representation of the silicon composite cathode material of the present invention；
Fig. 2 is the electron microscopic picture of silicon composite cathode material prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD figure of silicon composite cathode material prepared by the embodiment of the present invention 1；
Fig. 4 is the first charge-discharge curve of silicon composite cathode material prepared by the embodiment of the present invention 1；
Fig. 5 is the cycle performance curve of silicon composite cathode material prepared by the embodiment of the present invention 1.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the enforcement
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 60～120nm multi-walled carbon nano-tubes and fills volume ratio for nitre
Acid：Concentrated sulphuric acid=3:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, in being put into ultrasonic cleaner
Carry out ultrasonic oxidation 10h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port
Opening and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter is the silicon and fat of 10～30nm
Fat acid polyethylene glycol ester in mass ratio 20:10:0.5 is distributed in acetone, after mechanical agitation mixing 2h, is injected into high pressure-volume
In device, and pressure is passed through in nitrogen, plus bulk container thereto to 4.0x106Pascal, is kept for 24 hours, and nano-silicon is in capillary tube
Under active force and container pressure dual function, in being populated into CNT, last sucking filtration is dried to obtain black solid, grinds
Mill 1h obtains filling the CNT of nano-silicon to powder；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 850 DEG C, heating rate is 5 DEG C/min, and temperature retention time is 30min, after cooling, is obtained
The reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method being modified using mechanical-physical, is 10～30.0 μm of natural Scaly graphites and the first presoma by median particle diameter
In mass ratio 50:30 are placed in fusion in fusion machine, and setting rotating speed is 3000.0r/min, and cutter gap width is 0.5cm, is merged
0.5h obtains the second presoma；
(3) preparation of silicon composite cathode material
Using the method for liquid phase coating, by the second presoma and asphalt powder in mass ratio 80:50 dispersions in ethanol, are sprayed
Mist is dried, be subsequently placed in it is box in, be passed through nitrogen, be warming up to 1050.0 DEG C with 5.0 DEG C/min heating rates, be incubated 10.0h, from
Room temperature is so cooled to, is crushed, sieved and except magnetic, obtain particle diameter for 5.0-45.0 μm of novel high-capacity composite negative pole material.
Fig. 2 is the electron microscopic picture of silicon composite cathode material manufactured in the present embodiment, material granule can be observed and is uniformly dispersed；
Fig. 3 is the XRD figure of silicon composite cathode material manufactured in the present embodiment, and the diffraction maximum of more sharp graphite and silicon can be observed；Fig. 4
For the first charge-discharge curve of silicon composite cathode material manufactured in the present embodiment, material first charge-discharge efficiency height, is 90.8%；
Fig. 5 is the cycle performance curve of silicon composite cathode material manufactured in the present embodiment, and material circulation excellent performance is circulated 400 weeks and held
Amount conservation rate 91.5%.
Embodiment 2
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 60～120nm multi-walled carbon nano-tubes and fills volume ratio for nitre
Acid：Concentrated sulphuric acid=3:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, in being put into ultrasonic cleaner
Carry out ultrasonic oxidation 10h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port
Opening and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter is the silicon and Gu of 10～30nm
That glue in mass ratio 5:1:0.5 is distributed in acetone, after mechanical agitation mixing 2h, in being injected into high-pressure bottle, and to it
In be passed through in nitrogen, plus bulk container pressure to 4.0x106Pascal, is kept for 24 hours, last sucking filtration, is dried to obtain black and is consolidated
Body, grinding 1h to powder obtains filling the CNT of nano-silicon；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 850 DEG C, heating rate is 5 DEG C/min, and temperature retention time is 30min, after cooling, is obtained
The reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method coated using liquid phase chemical, is 10～30.0 μm of natural Scaly graphites and the first presoma by median particle diameter
In mass ratio 90：6 disperse in hexylene glycol solvent, are spray-dried, and obtain the second presoma.
(3) preparation of silicon composite cathode material
Second presoma is placed in rotary furnace, regulation speed of gyration is 3.0r/min, nitrogen is passed through, with 5.0 DEG C/min
Heating rate is warming up to 650 DEG C, is passed through acetylene gas, and flow is 1.0L/min, is incubated 2.0h, naturally cools to room temperature, obtains
Second presoma, crushes, sieves and except magnetic, obtains particle diameter for 5.0-45.0 μm of novel high-capacity composite negative pole material.
Embodiment 3
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 60～120nm multi-walled carbon nano-tubes and fills volume ratio for nitre
Acid：Concentrated sulphuric acid=3:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, in being put into ultrasonic cleaner
Carry out ultrasonic oxidation 10h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port
Opening and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter be the silicon of 10～30nm with it is poly-
Vinylpyrrolidone in mass ratio 40:20:0.5 is distributed in acetone, after mechanical agitation mixing 2h, is injected into high-pressure bottle
In, and pressure is passed through in nitrogen, plus bulk container thereto to 4.0x106Pascal, is kept for 24 hours, last sucking filtration, dry
To black solid, grinding 1h to powder, obtain filling the CNT of nano-silicon；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 850 DEG C, heating rate is 5 DEG C/min, and temperature retention time is 30min, after cooling, is obtained
The reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method being modified using mechanical-physical, is 10～30.0 μm of natural Scaly graphites and the first presoma by median particle diameter
In mass ratio 30:60 are placed in fusion in fusion machine, and setting rotating speed is 3000.0r/min, and cutter gap width is 0.5cm, is merged
0.5h obtains the second presoma；
(3) preparation of silicon composite cathode material
Using solid phase method for coating, by the second presoma and epoxy powder in mass ratio 90:20 are placed in VC efficiently mixes
In conjunction machine, regulation rotating speed is 3000.0r/min, mixes 0.5h, in being subsequently placed in batch-type furnace, nitrogen is passed through, with 5.0 DEG C/min liters
Warm ramp is incubated 10.0h to 800.0 DEG C, naturally cools to room temperature, crushes, sieves and except magnetic, obtains particle diameter for 5.0-
45.0 μm of NEW TYPE OF COMPOSITE negative materials.
Embodiment 4
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 60～120nm multi-walled carbon nano-tubes and fills volume ratio for nitre
Acid：Concentrated sulphuric acid=3:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, in being put into ultrasonic cleaner
Carry out ultrasonic oxidation 10h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port
Opening and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter be the silicon of 10～30nm with it is poly-
Vinylpyrrolidone in mass ratio 10:5:0.5 is distributed in acetone, after mechanical agitation mixing 2h, is injected into high-pressure bottle
In, and pressure is passed through in nitrogen, plus bulk container thereto to 4.0x106Pascal, is kept for 24 hours, last sucking filtration, dry
To black solid, grinding 1h to powder, obtain filling the CNT of nano-silicon；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 850 DEG C, heating rate is 5 DEG C/min, and temperature retention time is 30min, after cooling, is obtained
The reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method coated using liquid phase chemical, is 10～30.0 μm of natural Scaly graphites and the first presoma by median particle diameter
In mass ratio 35：15 disperse in propanol solvent, are spray-dried, and obtain the second presoma.
(3) preparation of silicon composite cathode material
Using solid phase method for coating, by the second presoma and asphalt powder in mass ratio 50:77 are placed in VC high efficient mixers
In, regulation rotating speed is 3000.0r/min, mixes 0.5h, in being subsequently placed in batch-type furnace, is passed through nitrogen, is heated up with 5.0 DEG C/min fast
Rate is warming up to 950.0 DEG C, is incubated 10.0h, naturally cools to room temperature, crushes, sieves and except magnetic, obtains particle diameter for 5.0-45.0 μm
Novel high-capacity composite negative pole material.
Embodiment 5
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 140～200nm multi-walled carbon nano-tubes and fills volume ratio for nitre
Acid：Concentrated sulphuric acid=1:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, in being put into ultrasonic cleaner
Carry out ultrasonic oxidation 6h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port and open
Mouth and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter be 60～150nm silicon with
Sodium lauryl sulphate in mass ratio 10:5:0.5 is distributed in ether, after mechanical agitation mixing 12h, is injected into high pressure-volume
In device, and pressure is passed through in nitrogen, plus bulk container thereto to 6.0x106Pascal, is kept for 1 hour, last sucking filtration, dry
To black solid, grinding 4h to powder, obtain filling the CNT of nano-silicon；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 600 DEG C, heating rate is 0.5 DEG C/min, and temperature retention time is 120min, after cooling, is obtained
To the reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method coated using liquid phase chemical, is that 5～15.0 μm of Delaniums and the first presoma press matter by median particle diameter
Amount compares 35：15 disperse in propanol solvent, are spray-dried, and obtain the second presoma.
(3) preparation of silicon composite cathode material
Using solid phase method for coating, by the second presoma and asphalt powder in mass ratio 50:77 are placed in VC high efficient mixers
In, regulation rotating speed is 500.0r/min, mixes 10h, in being subsequently placed in batch-type furnace, is passed through nitrogen, is heated up with 20.0 DEG C/min fast
Rate is warming up to 1200.0 DEG C, is incubated 0.5h, naturally cools to room temperature, crushes, sieves and except magnetic, obtains particle diameter for 5.0-45.0 μm
Novel high-capacity composite negative pole material.
Embodiment 6
The preparation of (1) first presoma
First, pretreatment process, intermediate value is added to for 40～80nm multi-walled carbon nano-tubes and fills volume ratio for nitric acid：
Concentrated sulphuric acid=2:In the flask of the mixed solution of 1 concentrated nitric acid/concentrated sulphuric acid, after stirring, it is put in ultrasonic cleaner
Row ultrasonic oxidation 12h, finally carry out sucking filtration and in vacuum drying oven 90 DEG C be dried 12h drying, that is, obtain pure, port and open
Mouth and defective oxide/carbon nanometer tube black powder；
Secondly, the filling work procedure of CNT, by the CNT after oxidation, median particle diameter is the silicon of 40～80nm and ten
Six alkyl trimethyl ammonium bromides in mass ratio 10:5:0.5 is distributed in hexanol, after mechanical agitation mixing 6h, is injected into height
In pressure vessel, and pressure is passed through in nitrogen, plus bulk container thereto to 1.0x106Pascal, is kept for 48 hours, last sucking filtration,
Black solid is dried to obtain, grinding 0.5h to powder obtains filling the CNT of nano-silicon；
Subsequently, high temperature reduction operation, filling nano-silicone wire/carbon nanotube is put in porcelain boat, loads tube furnace, in blanket of nitrogen
Under enclosing protection, thermal reduction process is carried out in 1000 DEG C, heating rate is 20 DEG C/min, and temperature retention time is 10min, after cooling, is obtained
To the reduction CNT of filling nano-silicon；
The preparation of (2) second presomas
The method coated using liquid phase chemical, is that 5～10.0 μm of native graphites and the first presoma press matter by median particle diameter
Amount compares 35：15 disperse in propanol solvent, are spray-dried, and obtain the second presoma.
(3) preparation of silicon composite cathode material
Using solid phase method for coating, by the second presoma and asphalt powder in mass ratio 50:77 are placed in VC high efficient mixers
In, regulation rotating speed is 2000.0r/min, mixes 5h, in being subsequently placed in batch-type furnace, nitrogen is passed through, with 0.5 DEG C/min heating rates
600.0 DEG C are warming up to, 5.0h is incubated, room temperature is naturally cooled to, are crushed, sieved and except magnetic, it is new for 5.0-45.0 μm to obtain particle diameter
Type high power capacity composite negative pole material.
Comparative example 1
Composite negative pole material is prepared according to method substantially the same manner as Example 1, difference is：When preparing presoma 1, no
Using high pressure filling technique, directly by the CNT after oxidation, median particle diameter is the silicon and fatty acid polyglycol second two of 10～30nm
Alcohol ester in mass ratio 20:10:0.5 is distributed in acetone, obtains nano-silicon after mechanical agitation mixing 2h and answers with oxide/carbon nanometer tube
Used as the first presoma, in addition, remaining step is carried out compound by embodiment 1.
Electrochemistry cycle performance is tested using following methods：By negative material, conductive agent and binding agent by mass percentage
94：1：5 in a solvent mix their dissolvings, and control solid content is coated in copper foil current collector, vacuum drying, system 50%
Obtain cathode pole piece；Then tertiary cathode pole piece, the LiPF6/EC+DMC+EMC (v/v of 1mol/L for being prepared by traditional maturation process
=1:1:1) electrolyte, Celgard2400 barrier films, shell assemble 18650 cylinder cells using conventional production process.Cylinder
The charge-discharge test of battery on Wuhan Jin Nuo Electronics Co., Ltd.s LAND battery test systems, in normal temperature condition, 0.2C constant currents
Discharge and recharge, charging/discharging voltage is limited in 2.75～4.2V.
The correlated performance data of embodiment 1-6 and comparative example 1 is listed in the table below in 1.
Table 1
As it can be seen from table 1 negative material prepared by the method for the invention has excellent chemical property, circulation is steady
It is fixed.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (47)
1. a kind of silicon composite cathode material, it is characterised in that the negative material is nucleocapsid structure, and kernel is by graphite and coating
Constitute in the silico-carbo nanotube complex of graphite surface, shell is conductive carbon material clad；
Silicon in the silico-carbo nanotube complex is filled in CNT footpath and its surface；
The silicon composite cathode material siliceous 1～20wt%, 5～40wt% of CNT, 30～90wt% of graphite, conductive carbon material
Material 4-50wt%；
Silicon is nano-silicon in the silicon composite cathode material, and median particle diameter is 10.0～60.0nm.
2. negative material according to claim 1, it is characterised in that the median particle diameter of the silicon composite cathode material is
5.0～45.0 μm.
3. negative material according to claim 2, it is characterised in that the median particle diameter of the silicon composite cathode material is
8.0～35.0 μm.
4. negative material according to claim 3, it is characterised in that the median particle diameter of the silicon composite cathode material is
10.0～25.0 μm.
5. negative material according to claim 1, it is characterised in that the specific surface area of the silicon composite cathode material is
1.0～20.0m2/g。
6. negative material according to claim 5, it is characterised in that the specific surface area of the silicon composite cathode material is
1.5～8.0m2/g。
7. negative material according to claim 1, it is characterised in that the powder body compacted density of the silicon composite cathode material
For 1.0～2.0g/cm3。
8. negative material according to claim 7, it is characterised in that the powder body compacted density of the silicon composite cathode material
For 1.1～1.7g/cm3。
9. negative material according to claim 1, it is characterised in that the graphite is natural Scaly graphite, natural cryptocrystal
Matter graphite, native crystal veiny graphite, the combination of a kind of Delanium or at least 2 kinds.
10. negative material according to claim 1, it is characterised in that the graphite is shaped as lamellar, spherical bulk
Or spherical a kind or at least 2 kinds of combination.
11. negative materials according to claim 1, it is characterised in that the median particle diameter of the graphite is 5.0～30.0 μ
m。
12. negative materials according to claim 11, it is characterised in that the median particle diameter of the graphite is 8.0～25.0 μ
m。
13. negative materials according to claim 12, it is characterised in that the median particle diameter of the graphite is 10.0～20.0
μm。
The preparation method of the silicon composite cathode material described in a kind of 14. claim 1, comprises the following steps：
(1) nano-silicon is combined with CNT using high pressure completion method, obtains the first presoma；
(2) first presoma is coated in into graphite surface, obtains the second presoma；
(3) second presoma is carried out into coating modification, is sintered, obtain silicon composite cathode material.
15. preparation methoies according to claim 14, it is characterised in that step is carried out after (3)：Step (4) is by step (3)
The composite negative pole material for obtaining is crushed, sieves and except magnetic, obtain the silicon composite cathode material that median particle diameter is 5.0～45.0 μm.
16. preparation methoies according to claim 14, it is characterised in that the high pressure completion method prepares nano-silicon composite carbon
Nanotube is comprised the following steps：CNT pretreatment, carbon nano-tube filled, high temperature reduction.
17. preparation methoies according to claim 16, it is characterised in that the CNT pre-treatment step is：Room temperature
Under, CNT is added in the flask equipped with concentrated nitric acid/concentrated sulphuric acid mixed liquor, being subsequently placed in ultrasonic cleaner is carried out
6～12h of ultrasonic oxidation, finally carries out sucking filtration, is dried to obtain oxide/carbon nanometer tube.
18. preparation methoies according to claim 17, it is characterised in that described CNT be single-walled pipe, double-wall pipe,
1 kind or at least 2 kinds of mixing in multi-walled pipes.
19. preparation methoies according to claim 17, it is characterised in that the average caliber of the CNT be 40～
200nm。
20. preparation methoies according to claim 17, it is characterised in that the concentrated nitric acid and concentrated sulfuric acid volume ratio be 1～
3:1。
21. preparation methoies according to claim 16, it is characterised in that the carbon nano-tube filled step is：Will oxidation
CNT afterwards, nano-silicon, dispersant are added in organic solvent, after mixing, in being injected into high-pressure bottle, and to it
In be passed through noble gases, increase container pressure, kept for 1～48 hour, last sucking filtration is dried to obtain black solid, is ground to powder
End, obtains the CNT of nano-silicon filling.
22. preparation methoies according to claim 21, it is characterised in that the dispersant is sodium tripolyphosphate, six inclined phosphorus
Sour sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, cellulose derivative, polyacrylamide,
Guar gum, fatty acid polyethylene glycol ester, cetyl trimethylammonium bromide, Polyethylene Glycol to isooctyl phenyl ether, polyacrylic acid,
1 kind in polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate dehydration, p-ethylbenzoic acid and Polyetherimide or extremely
Few 2 kinds combination.
23. preparation methoies according to claim 21, it is characterised in that the organic solvent is a kind in alcohol, ketone and ether
Or at least 2 kinds of combination.
24. preparation methoies according to claim 21, it is characterised in that the noble gases be nitrogen, helium, neon,
1 kind or at least 2 kinds of combination in argon and xenon.
25. preparation methoies according to claim 21, it is characterised in that CNT, nano-silicon after the oxidation, point
The mass concentration of powder is respectively 5～40%, 1～20%, 0.1～1.0%.
26. preparation methoies according to claim 21, it is characterised in that the mixing is carried out by stirring.
27. preparation methoies according to claim 26, it is characterised in that, the mixing carries out 1～12h.
28. preparation methoies according to claim 21, it is characterised in that plus in bulk container pressure to 1.0 × 105～6.0 ×
106Pascal.
29. preparation methoies according to claim 21, it is characterised in that the time of the grinding is 0.5h～4h.
30. preparation methoies according to claim 16, it is characterised in that the CNT high temperature reduction step is：Will
The CNT of nano-silicon filling is put in heating response device, under atmosphere of inert gases protection, carries out thermal reduction process, is cooled down
Afterwards, the reduction CNT of nano-silicon filling is obtained.
31. preparation methoies according to claim 30, it is characterised in that the heating response device be vacuum drying oven, batch-type furnace,
Rotary furnace, roller kilns, pushed bat kiln or tube furnace.
32. preparation methoies according to claim 30, it is characterised in that the noble gases be nitrogen, helium, neon,
1 kind or at least 2 kinds of combination in argon and xenon.
33. preparation methoies according to claim 30, it is characterised in that gas flow is 0.1～5L/min.
34. preparation methoies according to claim 30, it is characterised in that the temperature of the thermal reduction is 600 DEG C～1000
DEG C, the time of thermal reduction is 10～120min.
35. preparation methoies according to claim 30, it is characterised in that the heating rate during thermal reduction be 0.5～
20.0℃/min。
36. preparation methoies according to claim 14, it is characterised in that step (2) coating is applied using mechanical-physical
Cover or liquid phase coating.
37. preparation methoies according to claim 14, it is characterised in that step (3) coating modification adopts gas phase bag
Cover modified, liquid phase coating to be modified or solid phase coating modification.
38. a kind of lithium ion batteries, it is characterised in that it includes the silicon composite cathode material described in any one of claim 1-13
Or silicon composite cathode material obtained in preparation method described in claim 14.
The preparation method of lithium ion battery described in a kind of 39. claim 38, wherein cathode pole piece are by by claim 1-13
Silicon composite cathode material described in any one or silicon composite cathode material obtained in preparation method described in any one of claim 14-37
Material, conductive agent and binding agent are by mass percentage (91～94):(1～3):(3～6) dissolving mixes in a solvent, is coated on copper
On paper tinsel collector, vacuum drying, be obtained.
40. preparation methoies according to claim 39, it is characterised in that the conductive agent is graphite powder and/or conductive nano
Liquid.
41. preparation methoies according to claim 40, it is characterised in that nano conductive liquid the receiving by 0.5-20wt%
Rice material with carbon element is constituted with dispersion solvent.
42. preparation methoies according to claim 41, it is characterised in that the nano-carbon material is Graphene, carbon nanometer
1 kind or at least 2 kinds of combination in pipe, carbon nano-fiber, fullerene, white carbon black and acetylene black.
43. preparation methoies according to claim 40, it is characterised in that the graphite flake number of plies of the Graphene is 1-100.
44. preparation methoies according to claim 42, it is characterised in that the diameter of the CNT or carbon nano-fiber
For 0.2-500nm.
45. preparation methoies according to claim 42, it is characterised in that the particle diameter of the fullerene, white carbon black or acetylene black
For 1-200nm.
46. preparation methoies according to claim 39, it is characterised in that the binding agent is polyimide resin, propylene
1 kind of acid resin, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose or butadiene-styrene rubber or at least 2 kinds of combination.
47. preparation methoies according to claim 39, it is characterised in that the solvent is N-Methyl pyrrolidone, diformazan
1 kind or at least 2 kinds of combination in base Methanamide, acetone or methyl ethyl ketone.
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| CN105185961B (en) * | 2015-08-14 | 2018-10-16 | 深圳市国创新能源研究院 | Battery negative electrodes, Si carbon-base lithium ion battery and its application |
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| CN106469814B (en) * | 2016-04-14 | 2019-11-29 | 山东圣泉新能源科技有限公司 | A kind of covering, negative electrode material, lithium ion battery and preparation method thereof |
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| CN109360962B (en) * | 2018-10-24 | 2021-02-12 | 郑州中科新兴产业技术研究院 | High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof |
| CN109755522A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of lithium ion battery high-energy density and high power density negative electrode material and preparation method |
| CN109904435B (en) * | 2019-04-08 | 2021-11-30 | 深圳大学 | Preparation method of composite electrode material and composite electrode material |
| CN111841383B (en) * | 2019-04-26 | 2022-07-12 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN114203998A (en) * | 2020-09-02 | 2022-03-18 | 北京清创硅谷科技有限公司 | Carbon-silicon composite secondary particle and preparation method thereof |
| CN112125304B (en) * | 2020-09-25 | 2022-08-23 | 福建师范大学 | Metal oxide modified micro-nano silicon-graphite composite negative electrode material and preparation method thereof |
| CN112349915B (en) * | 2020-10-28 | 2021-11-12 | 贝特瑞新材料集团股份有限公司 | Graphite composite material, preparation method and application thereof |
| CN113594440B (en) * | 2021-07-08 | 2023-07-18 | 天津大学 | Lithium ion battery anode material with multistage conductive structure and preparation method thereof |
| WO2023240381A1 (en) * | 2022-06-13 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and preparation method therefor, secondary battery, and electric apparatus |
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| JP5257740B2 (en) * | 2008-01-30 | 2013-08-07 | 東海カーボン株式会社 | Composite carbon material for negative electrode material of lithium secondary battery and method for producing the same |
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