CN105161671A - Preparation method for tin-carbon composite negative material - Google Patents
Preparation method for tin-carbon composite negative material Download PDFInfo
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- CN105161671A CN105161671A CN201510480851.5A CN201510480851A CN105161671A CN 105161671 A CN105161671 A CN 105161671A CN 201510480851 A CN201510480851 A CN 201510480851A CN 105161671 A CN105161671 A CN 105161671A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method for a tin-carbon composite negative material. An outer layer of the tin-carbon composite negative material is a composite cladding layer jointly formed by asphalt, resin and tin powder, and an inner layer is the tin-carbon composite negative material which is composed of graphite and has a core-shell structure. In the tin-carbon composite material prepared according to the method, high specific capacity characteristic of tin is maintained, meanwhile, a modification effect on the graphite is played, the overall cyclic stability of the material is improved, the energy density of the negative material of a lithium ion battery is improved, thus, the negative material has higher specific capacity than the carbon negative material commonly used in the lithium ion battery in the current market, and the increasing energy density requirement of various portable electric devices on the battery is met.
Description
Technical field
The present invention relates to field of lithium ion battery, be specially a kind of preparation method of the tin carbon compound cathode materials for lithium ion battery negative, tin carbon compound cathode materials skin prepared by the method is the superpacket coating jointly formed by pitch and resin, glass putty, and internal layer is the tin carbon compound cathode materials with nucleocapsid structure of graphite composition.
Background technology
Since nineteen ninety Sony corporation of Japan take the lead in succeeding in developing lithium ion battery and by its commercialization since, lithium ion battery obtains fast development.Nowadays lithium ion battery has been widely used in civilian and military every field.Along with the continuous progress of science and technology, the performance of people to battery proposes more higher requirements: the miniaturization of electronic equipment and individualized development, and the specific energy needing battery to have less volume and Geng Gao exports; Aero-Space energy requirements battery has cycle life, the security performance of better low temperature charge-discharge performance and Geng Gao; Electric automobile needs the battery of Large Copacity, low cost, high stability and security performance.
What current commercial Li-ion battery negative material adopted is graphite-like material with carbon element, and having lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy, the demand of growing high-energy Portable power source can not be met.Meanwhile, when graphite is as negative material, in first charge-discharge process, form one deck solid electrolyte film (SEI) on its surface.Solid electrolyte film is the formation that react to each other such as electrolyte, negative material and lithium ion, irreversibly consumes lithium ion, is to form the main factor of of irreversible capacity; It two is in the process of Lithium-ion embeding, electrolyte easily and its be embedded in the process of moving out altogether, electrolyte is reduced, the gaseous product generated causes graphite flake layer to peel off, especially containing in the electrolyte of PC, graphite flake layer comes off new for formation interface, causes further SEI to be formed, irreversible capacity increases, and cyclical stability declines simultaneously.And the degree of order of the amorphous carbon formed after resin polymers pyrolysis is low, structure comparison is loose, and lithium ion can embed relatively freely wherein and deviate from and can not produce large impact to its structure.
In addition, tin is a kind of negative material being hopeful to replace material with carbon element most, this is because tin has the peak capacity up to 4200mAh/g; And there is the stable discharge platform being similar to graphite.But with other high power capacity Metal Phase seemingly, the non-constant of cycle performance of tin, can not carry out normal charge and discharge cycles.When tin uses as negative material, can along with huge change in volume, cause the avalanche of material structure and peeling off of electrode material and make electrode material lose electrical contact, thus cause the cycle performance of electrode sharply to decline, finally cause electrode failure, therefore in lithium-ions battery, be difficult to practical application.Research shows, the tin of small particle diameter or its alloy all improve a lot on capacity or on cycle performance, when the particle of alloy material reaches nanoscale, volumetric expansion in charge and discharge process can alleviate greatly, performance also can increase, but nano material has larger surface energy, easily reunites, efficiency for charge-discharge can be made on the contrary to reduce and accelerate the decay of capacity, thus counteract the advantage of nano particle; The tin film adopting various deposition process to prepare can extend the cycle life of material to a certain extent, but can not eliminate the irreversible capacity first that it is higher, thus constrain the practical of this material.Another research tendency improving tin negative pole performance is exactly prepare composite material or the alloy of tin and other material, and wherein, the tin/carbon composite prepared in conjunction with the stability of material with carbon element and the height ratio capacity characteristic of tin shows huge application prospect.The preparation technology of existing tin/carbon composite mainly contains following several respects:
(1) mechanical ball milling: this method is that nano composite material is worn in direct kick after glass putty and carbon mixing.Glass putty and material with carbon element, can be mutually dispersed with nanoscale after efficient mechanical ball milling.Owing to surrounding material with carbon element around the glass putty of nano-scale, thus the change in volume because slotting lithium and de-lithium cause can be suppressed, improve the cycle performance of tin material to a certain extent.Along with the increase of Theil indices, the specific capacity of tin/carbon composite increases, but cyclical stability is deteriorated.Meanwhile, in composite material, the crystal structure of two kinds of components, size and compatibility decide the final performance of material.The subject matter that composite material prepared by this method exists is: because specific area is comparatively large, and can not prevent the micro-oxidation in mechanical milling process completely, therefore irreversible capacity is large first;
(2) high polymer parcel glass putty carries out carbonization: this method can be dispersed in glass putty in carbon matrix well, improves its cycle performance; But be amorphous carbon due to what formed after high polymer carbonization, can not embody stability and the conductivity of graphitic carbon material completely, and may increase the irreversible capacity first of composite material due to impalpable structure, therefore combination property is unsatisfactory;
(3) pitch carries out carbonization as after binding agent bonding glass putty and graphite: pitch not only as binding agent evenly in conjunction with graphite and tin, and can also play the effect of face coat after carbonization.But pitch low-temperature carbonization product is similarly impalpable structure, and pitch is limited as the cementation of binding agent to carbon and tin, and therefore prepared material property needs to improve further;
(4) CVD coating: directly utilize CVD method, carries out carbon film parcel to tin or tin/carbon mix.After coating, the cycle performance of tin improves, but due to coating amount less, can not embody carbon base body effect completely, prepared material property is poor, but the material prepared by this method can study tin/carbon composite storage lithium mechanism.
More than show, at present in the coating modification process of material, all only hard charcoal precursor of independent resin-coated class or pitch class soft charcoal precursor.Adopt resinae as clad material, major advantage is resin good fluidity at low temperatures, can not only clad surface, and penetrate into material granule inside easily via micropore, useful to the tap density and electronic conductivity that improve material, can also by heating, introduce the solidification of the method such as catalyst or Ultraviolet radiation, distortion can not be melted in resin pyrolytic process, also obvious expansion can not be produced, but also there are some problems, mainly contain: the Carbon Materials yield obtained by resin pyrolysis is on the low side, enbrittle, in resin pyrolytic process, fugitive constituent is many, specific area is higher, the cohesive force of resin is stronger, be easy to cause coated particle to bond together, the destruction of coating layer is easily caused when pulverizing after heat treatment.These problems above, have impact on the compressibility of the cycle efficieny of resin-coating material, cyclical stability and electrode.Adopt pitch, petroleum tar, coal tar or their mixture as clad material, the asphalt pyrolysis charcoal specific area more coated than From Resin Char is little, to get well with the affinity of material, structure is more firm, but pitch-coating is out of shape because of fusing in heating process, consumption too much also easily causes the mutually bonding of clad material particle, consumption is very few easily cause coated uneven, and be easy in heating process expand, affect the electrical property of material.
Summary of the invention
The object of this invention is to provide a kind of preparation method of tin carbon compound cathode materials, this tin carbon compound cathode materials skin is the superpacket coating jointly formed by pitch and resin, glass putty, and internal layer is the tin carbon compound cathode materials with nucleocapsid structure of graphite composition.Tin carbon composite prepared by this method maintains the height ratio capacity characteristic of tin, modifying function is served to graphite simultaneously, add the cyclical stability of material monolithic, improve the energy density of the negative material of lithium ion battery, make this negative material have higher specific capacity than carbon negative pole material conventional in current commercial lithium ion battery, meet the energy density requirement that all kinds of portable power consumption equipment improves day by day to battery.
For achieving the above object, the present invention adopt following technical scheme to realize.
A preparation method for tin carbon compound cathode materials, comprises the following steps:
1, the pitch of softening point between 100 DEG C ~ 300 DEG C and the resin of softening point between 50 DEG C ~ 150 DEG C are joined by the weight ratio of 1:1.5 ~ 4 in the kneading still with heating and agitating device, be heated to pitch with the speed of 10 ~ 40 DEG C/min and resin is all fused into liquid;
2, then add the curing agent accounting for amount of resin 2% ~ 5%, under inert gas shielding, be constantly stirred to various component and mix;
3, according to resin and pitch total weight: the weight of graphite is that the ratio of 1:4 ~ 20 takes graphite, join with stir and heating function mixing arrangement in, mixing speed is 60 ~ 180 revs/min, and heating-up temperature is 40 DEG C ~ 140 DEG C, and this temperature is a little less than the temperature of resin softening point;
4, according to graphite: glass putty: the ratio of dispersion solvent=10:0.5 ~ 2:1.5 ~ 6 takes glass putty and dispersion solvent, is joined in dispersion solvent by glass putty, and ultrasonic disperse evenly after join in step 3 graphite mixing arrangement, be uniformly mixed;
5, the liquid mixed in step 2 is passed through atomising device, joining step 4 is mixed with in the mixing arrangement of graphite and glass putty, in mixing after 2 ~ 5 hours, stopping is heated and under being cooled to normal temperature state according to the speed of 5 ~ 20 DEG C/min, now resin completes solidification;
6, by the powder of gained in step 5, under the protection of inert gas, be warming up to 700 ~ 900 DEG C with the speed of 1 ~ 5 DEG C/min, then be incubated 1 ~ 5h, Temperature fall, sieve after cooling and namely obtain adopting the tin carbon compound cathode materials obtained by the present invention.
In the present invention, the pitch described in step 1 comprises one or more the mixture in coal tar pitch, petroleum asphalt, modified coal tar pitch, mesophase pitch, the condensation polycyclic polynuclear aromatic hydrocarbon that obtained by asphalt modifier, and softening point is more than 100 DEG C.
In the present invention, the resin described in step 1 is thermoplastic resin, comprises one or more the mixture in furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin and polyformaldehyde methacrylate resin.
In the present invention, the time of the stirring described in step 1 is 80 ~ 130min, and the final temperature of heating is higher 30 ~ 40 DEG C than the most high softening-point of component medium pitch and resin.
In the present invention, the curing agent described in step 2 is hexamethylenetetramine, diethyl amino propylamine, trimethylhexamethylenediamine, two base triamine, one or more the mixture had in the thermosetting resin of solidification.
In the present invention, the graphite described in step 3 is a kind of in native graphite or Delanium or both mixtures, and average grain diameter is 5 ~ 30 μm, tap density>=0.75g/cm
3, specific area≤6.0m
2/ g.
In the present invention, the average grain diameter≤100nm of the glass putty described in step 4.
In the present invention, the dispersion solvent described in step 4 is ethanol, isopropyl alcohol, carbon disulfide, toluene, dimethylbenzene or with the one in the distilled water of decentralized medium.
In the present invention, what in step 5, atomization adopted is utilize the one in the atomising device of ultrasonic atomizatio, centrifugal atomizing, the work of high-pressure atomization principle.
In above-mentioned preparation method, described inert gas is one or both the gaseous mixture in nitrogen, argon gas, helium.
When graphite is as negative material, in first charge-discharge process, form one deck solid electrolyte film (SolidElectrolyteInterphase and SEI) on its surface.Solid electrolyte film is the formation that react to each other such as electrolyte, negative material and lithium ion, irreversibly consumes lithium ion, is to form the main factor of of irreversible capacity; It two is in the process of Lithium-ion embeding, electrolyte easily and its be embedded in the process of moving out altogether, electrolyte is reduced, the gaseous product generated causes graphite flake layer to peel off, especially containing in the electrolyte of PC, graphite flake layer comes off new for formation interface, causes further SEI to be formed, irreversible capacity increases, and cyclical stability declines simultaneously.And the degree of order of the amorphous carbon formed after phenolic resins pyrolysis is low, structure comparison is loose, lithium ion can embed relatively freely wherein and deviate from and can not produce large impact to its structure, therefore efflorescence is less likely to occur, RESEARCH OF PYROCARBON is coated on graphite periphery as one deck barrier simultaneously, effectively can stop the effect of organic solvent and graphite body, thus prevent the caused graphite linings of inserting altogether of lithium ion and electrolyte to peel off and efflorescence.But because resin is in heat treatment process, the Small molecular in resin is too much, and the surface of coated rear material can be caused in overflow process to produce too much space, cause coated after the specific area of graphite excessive and cause irreversible capacity first excessive.Adopt the compound coating material that pitch and mixed with resin are formed, Pyrolytic carbon coating is formed at graphite surface, not only make use of the advantage of pitch and resin simultaneously, also assures that both uniformities, operability, after Overheating Treatment, together with asphalt carbon and resin carbon are pinned at mutually, complementary not enough, improve the comprehensive electrochemical properties of coated graphite, different compound coating materials can also be prepared by regulating the ratio of pitch and resin simultaneously, thus control the specific area of Coating Graphite Particles, meet cyclicity and doubly forthright different requirements.
When glass putty is as negative active core-shell material, in charge and discharge process, the change in volume of particle is very large, causes tin particles efflorescence, the non-constant of electrode cycle.The present invention not only as binding agent evenly in conjunction with graphite and tin, and can also play the effect of face coat by the compound coating material of pitch and resin property after carbonization.The method improves the cycle performance of tin to a great extent.
With prior art, the invention has the beneficial effects as follows:
1, the innovative point that the present invention is the most outstanding is by after clad material presoma Combined Processing, more coated glass putty and graphite; Ensure that the uniformity that multiple clad material presoma mixes, simultaneously without any need for solvent, environmentally friendly; In addition, technique is simple, and cost is low, easy suitability for industrialized production;
2, the present invention is by adding a certain amount of resin curing agent to compound coating material, resin is after overcuring, skeletal support effect can be played, prevent carbonisation medium pitch from melting and powder occurs that adhesion is lumpd after causing carbonization, and need to carry out to it phenomenon that break process causes material coating layer to destroy;
3, the amorphous carbon that formed after high temperature cabonization of resin, to electrolyte, there is stronger corrosion resistance ability, simultaneously, the interlamellar spacing of amorphous carbon is larger, lithium ion can pass in and out fast, meet the requirement of lithium ion battery high power charging-discharging, the bulk effect that glass putty produces when discharge and recharge can be cushioned in the hole secondly formed after resin carbonation and space, ensures the overall stability of material;
4, the present invention and the hard charcoal precursor of independent resin-coated class or pitch class soft charcoal precursor as compared with clad material, there is obvious superiority, together with asphalt carbon and resin carbon are pinned at mutually, complementary not enough, effectively can improve the intensity of coating layer, ensure the cyclical stability of tin carbon composite.
Embodiment
Reaching object to make technological means of the present invention, creation characteristic, workflow, using method and effect is easy to understand, setting forth the present invention further below.
By mesophase pitch (softening point 250 DEG C) and phenolic resins (softening point 110 DEG C) according to 1:3(3.5Kg with 10.5Kg) ratio together with join in the kneading still of 20L, start intensification and be heated to 300 DEG C, after pitch and resin are all fused into liquid, then add the curing agent-hexamethylenetetramine of 0.315Kg according to the ratio of weight resin 3%, be constantly stirred to each component and mix, according to pitch and total resin weight: the ratio of graphite weight=1:9 takes the native graphite of 126Kg, add with stir and heating function mixing arrangement in, stir and be warming up to 100 DEG C, according to graphite: glass putty: the ratio of dispersion solvent=10:1.5:3 takes the alcoholic solution of glass putty that 18.9Kg average grain diameter is 50nm and 37.8 kilograms, after glass putty is joined alcoholic solution, disperseed by ultrasonic unit, after dispersion all has, add after in the device of above-mentioned admixed graphite and stir 120min, then the pitch will mixed, resin, the mixing material of curing agent is sprayed onto in graphite agitating device by ultrasonic atomizing device, until mixing material has all sprayed, after mixing 3 hours again, stop heating and under being cooled to normal temperature state according to the speed of 10 DEG C/min, now resin completes solidification, finally by the powder that mixes with the ramp to 900 DEG C of 5 DEG C/min, be incubated 1 hour, be then cooled to room temperature, obtain tin carbon compound cathode materials of the present invention through screening.
Using this electrode material as work electrode, lithium sheet is to electrode, 1MLiPF6/DMC:EC:DEC=1:1:1, and solution is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into simulated battery, with the current density discharge and recharge of 50mA/g.This electrode material discharge capacity first reach 425mAh/g, 100 times circulation after capacity still have 394mAh/g, conservation rate is 92.7%.
Embodiment 2
By coal tar pitch (softening point 120 DEG C) and phenolic resins (softening point 110 DEG C) according to 1:3(3Kg with 12Kg) ratio together with join in the kneading still of 20L, start intensification and be heated to 150 DEG C, after pitch and resin are all fused into liquid, then add the curing agent-trimethylhexamethylenediamine of 0.675Kg according to the ratio of weight resin 4.5%, be constantly stirred to each component and mix, according to pitch and total resin weight: the ratio of graphite weight=1:10 takes the native graphite of 150Kg, add with stir and heating function mixing arrangement in, stir and be warming up to 105 DEG C, according to graphite: glass putty: the ratio of dispersion solvent=10:2:4 takes the aqueous isopropanol of glass putty that 30Kg average grain diameter is 50nm and 60 kilograms, after glass putty is joined aqueous isopropanol, disperseed by ultrasonic unit, after dispersion all has, add after in the device of above-mentioned admixed graphite and stir 150min, then the pitch will mixed, resin, the mixing material of curing agent is sprayed onto in graphite agitating device by ultrasonic atomizing device, until mixing material has all sprayed, after mixing 2 hours again, stop heating and under being cooled to normal temperature state according to the speed of 15 DEG C/min, now resin completes solidification, finally by the powder that mixes with the ramp to 850 DEG C of 3 DEG C/min, be incubated 2 hours, be then cooled to room temperature, obtain tin carbon compound cathode materials of the present invention through screening.
This electrode material test condition as described in example 1 above, with the current density discharge and recharge of 50mA/g.The discharge capacity first of this electrode material reaches 451mAh/g, and the capacity after 100 circulations still has 426mAh/g, and conservation rate is 94.4%.
More than show and describe general principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (9)
1. a preparation method for tin carbon compound cathode materials, comprises the following steps:
(1) pitch of softening point between 100 DEG C ~ 300 DEG C and the resin of softening point between 50 DEG C ~ 150 DEG C are joined by the weight ratio of 1:1.5 ~ 4 in the kneading still with heating and agitating device, be heated to pitch with the speed of 10 ~ 40 DEG C/min and resin is all fused into liquid;
(2) then add the curing agent accounting for amount of resin 2% ~ 5%, under inert gas shielding, be constantly stirred to various component and mix;
(3) according to resin and pitch total weight: the weight of graphite is that the ratio of 1:4 ~ 20 takes graphite, join with stir and heating function mixing arrangement in, mixing speed is 60 ~ 180 revs/min, and heating-up temperature is 40 DEG C ~ 140 DEG C, and this temperature is a little less than the temperature of resin softening point;
(4) according to graphite: glass putty: the ratio of dispersion solvent=10:0.5 ~ 2:1.5 ~ 6 takes glass putty and dispersion solvent, is joined in dispersion solvent by glass putty, and ultrasonic disperse evenly after join in step 3 graphite mixing arrangement, be uniformly mixed;
(5) liquid mixed in step 2 is passed through atomising device, joining step 4 is mixed with in the mixing arrangement of graphite and glass putty, in mixing after 2 ~ 5 hours, stopping is heated and under being cooled to normal temperature state according to the speed of 5 ~ 20 DEG C/min, now resin completes solidification;
(6) by the powder of gained in step 5, under the protection of inert gas, be warming up to 700 ~ 1900 DEG C with the speed of 1 ~ 5 DEG C/min, then be incubated 1 ~ 5h, Temperature fall, sieve after cooling and namely obtain adopting the modified graphite cathode material obtained by the present invention.
2. the preparation method of a tin carbon compound cathode materials, it is characterized in that: the pitch described in step (1) comprises one or more the mixture in coal tar pitch, petroleum asphalt, modified coal tar pitch, mesophase pitch, the condensation polycyclic polynuclear aromatic hydrocarbon that obtained by asphalt modifier, and softening point is more than 100 DEG C.
3. the preparation method of a tin carbon compound cathode materials, it is characterized in that: the resin described in step (1) is thermoplastic resin, comprise one or more the mixture in furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin and polyformaldehyde methacrylate resin.
4. a preparation method for tin carbon compound cathode materials, is characterized in that: the time of the stirring described in step (1) is 80 ~ 130min, and the final temperature of heating is higher 30 ~ 40 DEG C than the most high softening-point of component medium pitch and resin.
5. a preparation method for tin carbon compound cathode materials, is characterized in that: the curing agent described in step (2) is hexamethylenetetramine, diethyl amino propylamine, trimethylhexamethylenediamine, two base triamine, one or more the mixture had in the thermosetting resin of solidification.
6. a preparation method for tin carbon compound cathode materials, is characterized in that: the graphite described in step (3) is a kind of in native graphite or Delanium or both mixtures, and average grain diameter is 5 ~ 30 μm, tap density>=0.75g/cm
3, specific area≤6.0m
2/ g.
7. a preparation method for tin carbon compound cathode materials, is characterized in that: the average grain diameter≤100nm of the glass putty described in step (4).
8. a preparation method for tin carbon compound cathode materials, is characterized in that: the dispersion solvent described in step (4) is ethanol, isopropyl alcohol, carbon disulfide, toluene, dimethylbenzene or with the one in the distilled water of decentralized medium.
9. a preparation method for tin carbon compound cathode materials, is characterized in that: what in step (5), atomization adopted is utilize the one in the atomising device of ultrasonic atomizatio, centrifugal atomizing, the work of high-pressure atomization principle.
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|---|---|---|---|
| CN201510480851.5A CN105161671A (en) | 2015-08-07 | 2015-08-07 | Preparation method for tin-carbon composite negative material |
| PCT/CN2016/087181 WO2017024903A1 (en) | 2015-08-07 | 2016-06-25 | Preparation method for tin-carbon composite negative electrode material |
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| CN201510480851.5A CN105161671A (en) | 2015-08-07 | 2015-08-07 | Preparation method for tin-carbon composite negative material |
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Cited By (7)
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| WO2017024903A1 (en) * | 2015-08-07 | 2017-02-16 | 田东 | Preparation method for tin-carbon composite negative electrode material |
| CN107689302A (en) * | 2016-08-03 | 2018-02-13 | 薛富盛 | Silver-colored carbon composite aqueous solution and preparation method thereof, silver-colored carbon recombiner unit, electric conductor, and the preparation method of electric conductor |
| CN108493437A (en) * | 2018-03-19 | 2018-09-04 | 福建翔丰华新能源材料有限公司 | A method of preparing tin carbon lithium ion negative material |
| CN108807873A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A method of preparing the tin carbon lithium ion negative material of copper Sb doped |
| CN111215633A (en) * | 2020-01-14 | 2020-06-02 | 大同新成新材料股份有限公司 | Method for preparing lithium ion negative electrode material by using tin graphene composite material |
| CN111916669A (en) * | 2020-07-30 | 2020-11-10 | 内蒙古凯金新能源科技有限公司 | Carbon cathode for lithium ion television and preparation method thereof |
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| WO2017024903A1 (en) * | 2015-08-07 | 2017-02-16 | 田东 | Preparation method for tin-carbon composite negative electrode material |
| CN107689302A (en) * | 2016-08-03 | 2018-02-13 | 薛富盛 | Silver-colored carbon composite aqueous solution and preparation method thereof, silver-colored carbon recombiner unit, electric conductor, and the preparation method of electric conductor |
| CN107689302B (en) * | 2016-08-03 | 2019-07-26 | 薛富盛 | The preparation method of silver-colored carbon composite aqueous solution |
| CN108493437A (en) * | 2018-03-19 | 2018-09-04 | 福建翔丰华新能源材料有限公司 | A method of preparing tin carbon lithium ion negative material |
| CN108493437B (en) * | 2018-03-19 | 2020-11-24 | 福建翔丰华新能源材料有限公司 | Method for preparing tin-carbon lithium ion negative electrode material |
| CN108807873A (en) * | 2018-04-25 | 2018-11-13 | 福建翔丰华新能源材料有限公司 | A method of preparing the tin carbon lithium ion negative material of copper Sb doped |
| CN108807873B (en) * | 2018-04-25 | 2021-06-25 | 深圳市翔丰华科技股份有限公司 | Method for preparing copper-antimony doped tin-carbon lithium ion negative electrode material |
| CN111215633A (en) * | 2020-01-14 | 2020-06-02 | 大同新成新材料股份有限公司 | Method for preparing lithium ion negative electrode material by using tin graphene composite material |
| CN112768644A (en) * | 2020-04-16 | 2021-05-07 | 西安越遴新材料研究院有限公司 | Modification method for coating silicon-carbon composite negative electrode material interface by using modified asphalt |
| CN111916669A (en) * | 2020-07-30 | 2020-11-10 | 内蒙古凯金新能源科技有限公司 | Carbon cathode for lithium ion television and preparation method thereof |
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