CN1304187A - Composite graphite negative electrode material for lithium cell and its preparation method - Google Patents
Composite graphite negative electrode material for lithium cell and its preparation method Download PDFInfo
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Abstract
The present invention relates to a composite graphite cathode material for making lithium ion cell and its preparation method. It is made up by using (wt%) 50-99% of graphite powder as core material, 1-50% of pyrolyzed carbon as external wrapping material and conducting agent whose dose is 0.01-10% of graphite weight and its specific surface area is 0.5-20 sq.m/g. It preparation method includes the following steps: wrapping the graphite powder particles with dissolved organic macromolecular polymer or organic compound, evaporating solvent, and high-temp. carbonizing at 500-1500 deg.C in protective atmosphere so as to obtain the invented product with low irreversible volume, high specific volume, high charging and discharging efficiency and good circulation property.
Description
The present invention relates to negative material and preparation method thereof in the lithium ion battery, more precisely composite graphite negative electrode material and preparation method thereof.
Graphite is important lithium ion battery negative material, and it has complete crystalline structure, and specific capacity is higher, and conductivity is better, has charge and discharge platform preferably, thereby has good security performance.But directly use the native graphite of graphite, particularly highly crystalline to do negative material, following shortcoming arranged:
1) owing to the height-oriented property of graphite crystal, the dynamics resistance of fast charging and discharging is bigger, thereby high-rate performance is undesirable.
2) Van der Waals force of graphite layers a little less than, expand when discharging and recharging and shrink, make that the cycle performance of graphite is not ideal enough.
3) graphite and organic electrolyte reaction, less stable.
After will suitably handling, could use in general graphite.
And high molecular polymer general stable higher to organic electrolyte of RESEARCH OF PYROCARBON after charing has cyclical stability preferably.But its conductivity is relatively poor, and irreversible capacity is bigger, and discharge voltage lacks the such platform of graphite.Therefore the researcher of many this respects attempts to coat one deck organic polymer RESEARCH OF PYROCARBON on graphite surface, form composite graphite-carbon composite, make it because the parcel of the RESEARCH OF PYROCARBON on the surface of graphite, the advantage that has both graphite and RESEARCH OF PYROCARBON can keep the reversible capacity of graphite height, and irreversible capacity is low, stability better, the characteristic of charge and discharge platform preferably, the good stability that keeps RESEARCH OF PYROCARBON to discharge and recharge again, characteristic such as orientation is low.So the researcher of this respect has done many research work, the patent documentation in this field has also appearred.
Japanese documentation publication number JP10-12241 has described the negative material that a kind of lithium rechargeable battery is used, it is to be nuclear with average grain diameter＜50 μ m graphite particles, with chemical vapour deposition technique at graphite particle surface deposition one deck charcoal, the composite material of a kind of graphite-charcoal element that forms, the specific surface of the plain composite material of graphite-charcoal is 1m
2Below/the g, the equilibrium adsorption water yield＜0.3wt%, the average grain diameter of graphite particle is more than 5 with the ratio of average thickness.Its preparation method is, used graphite raw material is native graphite and expanded graphite, through dry grinding or wet-milling, makes the graphite particle average grain diameter less than 50 μ m them, again with 1～25 μ m for well.Use chemical vapour deposition technique, adopt the organic substance of lower molecular weight to be evaporated to the graphite granule surface that needs coating, high temperature carbonization forms the plain composite material of compound graphite-charcoal, and it is 700-1300 ℃ that chemistry is steaming treatment temperature, is good with 900-1000 ℃ again.The raw material of used thermal decomposition charcoal element is styrene, benzene,toluene,xylene etc.But this method complex process, product quality are difficult to control, and utilances such as organic substance material styrene, benzene,toluene,xylene are low, and the product cost height is not suitable for large-scale production.
Japanese documentation JP9-330703 has described the manufacture method of lithium ion secondary battery cathode.The material of making negative pole is the plain composite material of graphite-charcoal, the preparation method of this composite material is the organic substance binding material to be dissolved in the excessive solvent, after the graphite crystallization micropowder mixes, evaporation removes and desolvates, and forms the composition of graphite and organic binding material.Above-mentioned composition is burnt till the compound carbon material that contains by the graphite-charcoal element of organic binding material charing under inert atmosphere or non-oxidizing atmosphere.Its final temperature of burning till is 500-1000 ℃, again with 700-900 ℃ better.Do not need to pulverize with graphite-carbonaceous product that this law generated.And the initial stage discharge capacity is low, about 240mAh/g, and the initial stage cyclical stability is poor, and irreversible capacity is too big, and is about 40%, more do not mention the situation of the plain compound carbon material of preparation graphite in enormous quantities-charcoal preparation in enormous quantities.
Japanese documentation JP10-12217 has described the plain compound carbon material of graphite/charcoal of using the low-crystalline charcoal element lower than graphite crystallization property to adhere on the graphite and forming, and the weight ratio of graphite and charcoal element is more than 81/19, below 95/5.The interlamellar spacing of used graphite is less than 0.338 nanometer, and crystalline size Lc is greater than wherein a kind of of the native graphite of 40 nanometers, pyrolytic graphite, vapor deposition graphite, Delanium.The interlamellar spacing of carbon material is more than 0.350 nanometer, and crystalline size Lc is less than 25 nanometers.Its preparation method is, graphite and organic binding material are mixed, and under high shear strength effect, forms and disperses compound composition, and burn till in inert atmosphere or nonoxidizing atmosphere the back that is shaped.Used organic binding material is natural or synthetic organic polymer material, comprises wherein one or more of monomer whose, oligomer, pitch class, hot plastic type resin, thermosetting resin.Firing temperature 500-1100 ℃.This method has solved the initial stage discharge capacity problem of unstable of aforementioned patent basically.But its irreversible capacity is too big, does not also mention the situation of long-term cyclical stability and preparation in enormous quantities.
From above-mentioned prior art, all do not reach satisfied effect.Prior art exists complex process, and product quality is wayward, product cost height, shortcoming such as poor stability, irreversible capacity are too big.
Purpose of the present invention just is to develop a kind of reversible capacity of graphite height that both kept, and irreversible capacity is low, the lithium ion battery composite graphite negative electrode material with good electro-chemical properties of good stability.
A further object of the present invention just is to work out the method for preparing above-mentioned material, and this method can be produced continuously, has avoided intensification, cooling, and the shortcoming of the interruption that heats up again production has reduced energy consumption, has reduced production cost.
A kind of composite graphite negative electrode material for lithium cell of the present invention, with the graphite powder particle is core material, RESEARCH OF PYROCARBON with organic high molecular polymer or organic compound is the external cladding material of graphite powder particle, in the coating process in the RESEARCH OF PYROCARBON conductive doped dose, this composite graphite negative electrode material contains graphite 50-99% percetage by weight, the RESEARCH OF PYROCARBON 1-50% percetage by weight of organic high molecular polymer or organic compound, the conductive agent that is mixed is the 0.01-10% of graphite weight, and the specific surface of composite graphite negative electrode material is 0.1～20 meters squared per gram.
Said conductive agent copper powder, silver powder, bronze, alloyed powder, carbon black, electrically conductive graphite, aquadag, acetylene black powder one or more powder wherein.Alloyed powder can be yellow gold powder, silver palladium alloy powder etc.Owing to added conductive agent in composite graphite negative electrode material, and make that the battery cycle life made from this material is long, the capacity height more helps heavy-current discharge.The specific surface of composite graphite negative electrode material of the present invention is 0.1～20 meters squared per gram, its specific surface is excessive, greater than 20 meters squared per gram, poor stability, the irreversible capacity height is had any problem on electrode is made, need the amount of binding agent big, and have influence on the performance of electrode, so its specific surface is 0.1～20 meters squared per gram, be good with 0.5～10 meters squared per gram again.The granularity D of composite graphite negative electrode material
50Be the 0.5-50 micron.
The preparation method of a kind of composite graphite negative electrode material for lithium cell of the present invention; organic high molecular polymer or organic compound are dissolved with corresponding solvent; again with the conductive agent powder of graphite powder and doping; by required amount; place the container that has the condensation retracting device; mixed 0.5-24 hour; elevated temperature is with the solvent distilled-to-dryness; stirring-granulating in the process of solvent evaporated; the outer surface that is formed on graphite powder particle is coated with one deck and contains the organic high molecular polymer of conductive agent or the graphite powder particle of organic compound; the outer surface of evaporate to dryness is coated with one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound places resistant to elevated temperatures container; in push-plate type or rotatable continuous tunnel furnace, feed protective gas; make to fill and be coated with the high-temperature resistant container that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent or organic compound and move in the heating zone of push-plate type or rotatable continuous tunnel furnace; make and be coated with that one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound heats up under the protection of protective atmosphere; rise to 500-1500 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace; under the protection of protective atmosphere; in the flat-temperature zone of continuous tunnel furnace, carry out high temperature cabonization; the temperature of flat-temperature zone is controlled at 500-1500 ℃ in the continuous tunnel furnace; in its flat-temperature zone in continuous tunnel furnace after mobile 0.1-10 hour; move into cooling area, drop to room temperature in the protection of protective atmosphere.
Said organic high molecular polymer is wherein a kind of of phenol-formaldehyde resin modified, epoxy resin, polyacrylonitrile, polystyrene, Vingon, Kynoar, polyvinyl alcohol, poly furfuryl alcohol, phenol formaldehyde resin; Organic compound is wherein a kind of of coal tar, pitch.The used in fact organic compound or the kind of organic high molecular polymer are very unimportant, just can use as long as at high temperature can RESEARCH OF PYROCARBON change into RESEARCH OF PYROCARBON.The used solvent that is used to dissolve above-mentioned organic high molecular polymer or organic compound can be acetone, toluene, dimethylbenzene, chlorobenzene, oxolane, butyl acetate, N, dinethylformamide, N-methyl pyrrolidone, chloroform and their derivative thereof, water.Different organic high molecular polymers dissolves with different solvents, and organic high molecular polymer dissolves with its corresponding solvent in other words, and organic compound also is like this.For example used for epoxy resin acetone or butyl acetate dissolving, the dissolving of polyvinyl-chloride use chloroform, polystyrene dissolves with toluene, polyacrylonitrile N, dinethylformamide or N-methyl pyrrolidone dissolve, and Kynoar is also used N, dinethylformamide or the dissolving of N-methyl pyrrolidone.This is the usual knowledge that the one of ordinary skill in the art all knows.Organic high molecular polymer or the organic compound concentration in solvent is to contain 1～200 gram organic high molecular polymer or organic compound in 100 milliliters of solvents to be advisable.When preparation composite graphite negative electrode material product, the amount of the material quantity of used graphite and used conducting powder can directly take by weighing.And will be under the situation that does not add graphite, conductive agent powder obtaining the RESEARCH OF PYROCARBON amount by above-mentioned whole process of preparation, organic high molecular polymer or organic compound coal tar, the needed amount of pitch learn the amount that should add organic high molecular polymer or the amount of organic compound.So the weight of the product that the composite graphite negative electrode material product made from this method draws deducts the amount of material quantity with the conductive agent powder that is added of the graphite that is added, and draw the amount of RESEARCH OF PYROCARBON after weighing, and calculate the content of each composition in the product.
Used raw material graphite can be electrographite or native graphite, and its suitable particle size range is to be controlled at 0.1-100 μ m for well, and is better with 1-40 μ m again.
Used conductive agent powder is copper powder, silver powder, bronze, alloyed powder, carbon black, electrically conductive graphite, aquadag, acetylene black powder one or more powder wherein.Used alloyed powder can be yellow gold powder, silver palladium alloy powder etc.The particle size range of conductive agent with the 0.01-50 micron for well.
With raw material organic high molecular polymer or organic compound with the corresponding solvent dissolving after, again with the graphite powder and the conductive agent powder that will mix, in a quantity as required, place the container that has the condensation retracting device under 10-50 ℃ temperature them, mixing speed with 1-5000 rev/min, after mixing 0.1-24 hour, elevated temperature is to 51-200 ℃, stirring-granulating in the evaporate to dryness process, until the organic high molecular polymer that will dissolve or the solvent distilled-to-dryness of organic compound, mixing speed during its stirring-granulating is 1-5000 rev/min, has so just formed to be coated with one deck to contain the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound on the outer surface of graphite powder particle.And in the process of evaporate to dryness, the solvent condenses that steams is reclaimed so that recycle.
Outer surface is coated with one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound places resistant to elevated temperatures container.Used high-temperature resistant container can be alundum (Al (being aluminium oxide) crucible, graphite crucible, ceramic crucible, silica crucible a kind of crucible wherein.To be coated with the thickness that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent powder or organic compound be 0.1-50 centimetre to the outer surface of evaporate to dryness in resistant to elevated temperatures container, better with 1-10 centimetre again.Its thickness reduces output less than 0.1 centimetre greatly, if its thickness greater than 50 centimetres, influences the quality of product again.
Feed protective gas in plug-type or rotatable continuous tunnel furnace, said protective gas is to add an amount of reducibility gas in inert gas or the indifferent gas.Inert gas is nitrogen, argon gas, helium a kind of inert gas wherein.Can add an amount of reducibility gas in inert gas, the reducibility gas that is added can be hydrogen or carbon monoxide, and the hydrogen that is added or the amount of carbon monoxide are the 0.1-50% percentage by volume of protective gas.Protective gas feed flow in push-plate type or the rotatable continuous tunnel furnace be the 10-10000 liter/hour, again with 100-5000 liter/hour for well.The low-temperature zone below 300 ℃ at heating zone can adopt an amount of oxidizing gas oxygen or the air of adding in inert gas, can impel organic high molecular polymer crosslinked like this, improves carbonation rate.The oxidizing gas oxygen that is added in inert gas or the amount of air are the 0.1-50% percentage by volume of protective gas, its flow be the 10-10000 liter/hour, again with 100-5000 liter/hour for well.
Make to fill and be coated with the high-temperature resistant container that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent powder or organic compound and move; enter in the heating zone of push-plate type or rotatable continuous tunnel furnace; make and be coated with that one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound heats up under the protection of protective atmosphere; programming rate is 0.1～25 ℃/minute; rise to 500～1500 ℃; again it is moved in the flat-temperature zone in the continuous tunnel furnace; under the protection of protective atmosphere; in continuous tunnel furnace, carry out high temperature carbonization; the temperature of flat-temperature zone is controlled at 500-1500 ℃ in the continuous tunnel furnace; in its flat-temperature zone in continuous tunnel furnace after mobile 0.1-10 hour; move into cooling area, the speed of cooling is 0.5～50 ℃/minute.Filling in heating zone, flat-temperature zone, cooling area and being coated with the translational speed of high-temperature resistant container that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent powder or organic compound is 0.1～50 centimeters/minute, reduces to room temperature.Preferably will reduce to room temperature be coated with one deck contain conductive agent RESEARCH OF PYROCARBON the composite graphite material product with commercially available be that the airslide disintegrating mill of crushing chamber inner lining material is pulverized product with the corundum, the scope that makes the meso-position radius (D50) of its product is 0.5-50 μ m, and the 1-25 μ m with the scope of its meso-position radius (D50) is good again.The charging rate by regulating airslide disintegrating mill and the pressure of air-flow are controlled the granularity of product.
In order to detect the performance of composite graphite negative electrode material for lithium cell of the present invention, the method with the those of ordinary skill under this area is all known is assembled into flat test cell with it and tests.With composite graphite negative electrode material for lithium cell 85-92% of the present invention (percetage by weight), binding agent PVDF (Kynoar) 8-15%, mix furnishing pulpous state (can also add conductive agent acetylene black 0-5% percetage by weight), be coated on the two sides of Copper Foil, at air drying, make negative pole.Electrode is formed test cell for the lithium sheet metal.Electrolyte is 1MLiPF
6/ EC+DMC etc., EC are ethylene carbonate, and DMC is a dimethyl carbonate.Charging and discharging currents density is 0.5A/cm
2, discharging and recharging upper and lower limit voltage is 0～1.5V, specific capacity computational methods C=mA * h/g lives, wherein C: and specific capacity, temperature is 25 ± 2 ℃, the constant current alternating current test instrument that computerizeds control carries out battery data collection and process control.
The advantage of the product of composite graphite negative electrode material for lithium cell of the present invention is:
1. product of the present invention has excellent electrochemical properties, the reversible capacity height that had both kept graphite, irreversible capacity is low, good stability, the advantage that has had both graphite and RESEARCH OF PYROCARBON, the characteristic of charge and discharge platform is preferably arranged, the good stability that has kept RESEARCH OF PYROCARBON to discharge and recharge again, characteristic such as orientation is low.With the lithium ion battery specific capacity height that product of the present invention is made, first charge-discharge efficiency height, good cycle.
2. owing to the conductive agent that mixed in the RESEARCH OF PYROCARBON, improve the conductivity of RESEARCH OF PYROCARBON coating layer, further improved the specific capacity and the charge-discharge performance of composite graphite.
The advantage of method of the present invention is:
1. because method of the present invention is carried out mobile carbonization in the flat-temperature zone of continuous tunnel furnace, can produce continuously, guaranteed the stability of consistency of product and production technology, avoided intensification, cooling again, again the shortcoming of the interruption production technology of Sheng Wening, reduced energy consumption, save the energy, reduced production cost of products, improved production efficiency, equipment investment is low, can produce on a large scale again.
2. the properties of product of producing with the inventive method are good, good stability.
3. adopted comminution by gas stream, the milling efficiency height, pure pollution can be controlled the size and the distribution thereof of granularity again effectively, and can carry out the adjustment and the control of granularity as required.
The cycle performance curve of Fig. 1 composite graphite negative electrode material
Among the figure, ordinate is specific capacity (mAh/g), and abscissa is a cycle-index.
-■-be embodiment 2-◆-be embodiment 3
The transmission electron microscope picture of Fig. 2 composite graphite negative electrode material
Among the figure, the clear zone is the crystalline texture of graphite, and the dark space is the undefined structure of RESEARCH OF PYROCARBON.
Below with embodiment composite graphite negative electrode material for lithium cell of the present invention and preparation method thereof is further described, will help material of the present invention and the preparation method of this material and advantage thereof are done further to understand.Protection scope of the present invention is not subjected to the restriction of these embodiment, and protection scope of the present invention is decided by claim.
Embodiment 1
Composite graphite negative electrode material for lithium cell in the present embodiment, with the native graphite powder particles is core material, with organic high molecular polymer polyacrylonitrile RESEARCH OF PYROCARBON is the external cladding material of graphite powder particle, conductive doped dose of acetylene black in the RESEARCH OF PYROCARBON in the coating process, this composite graphite negative electrode material contains native graphite 90% percetage by weight, the RESEARCH OF PYROCARBON that contains the organic high molecular polymer polyacrylonitrile accounts for 10% percetage by weight, the conductive agent acetylene black of being mixed is 1% of native graphite amount, and the specific surface of composite graphite negative electrode material is 5 meters squared per gram.
Its method for making is, claim the organic high molecular polymer polyacrylonitrile 20 grams, be dissolved in N, in the dinethylformamide (or N-methyl pyrrolidone), again with 90 gram natural graphite powders and the 0.9 acetylene black powder that restrains, place the container that has the condensation retracting device, stirred 5 hours, intensification is with solvent N, dinethylformamide (or N-methyl pyrrolidone) distilled-to-dryness, at solvent evaporated N, stirring-granulating in the process of dinethylformamide (or N-methyl pyrrolidone), the outer surface that is formed on the native graphite powder particles is coated with the native graphite powder particles of the organic high molecular polymer polyacrylonitrile that contains conductive agent acetylene black powder.Outer surface is coated with the native graphite powder particles of one deck organic high molecular polymer polyacrylonitrile; place resistant to elevated temperatures container alundum (Al crucible; in push-plate type or rotatable continuous tunnel furnace, feed the protective gas argon gas; make to fill and be coated with the graphite powder particle high-temperature resistant container alundum (Al crucible that one deck contains the organic high molecular polymer polyacrylonitrile of conductive agent acetylene black powder and move; enter the heating zone in push-plate type or the rotatable continuous tunnel furnace; make and be coated with the organic high molecular polymer polyacrylonitrile native graphite powder particles that one deck contains conductive agent acetylene black powder and under the protection of protective atmosphere, be warming up to 1200 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace; under the protection of the atmosphere of protective gas argon gas; in the flat-temperature zone of continuous tunnel furnace, carry out high temperature cabonization; flat-temperature zone in continuous tunnel furnace is controlled at 1200 ℃; the time of moving in its flat-temperature zone in continuous tunnel furnace is 2 hours; again it is moved into cooling area, in protective atmosphere, reduce to room temperature.The product of present embodiment makes that its specific capacity is 340mAh/g behind the battery.
Embodiment 2
Composite graphite negative electrode material for lithium cell in the present embodiment, with the native graphite powder particles is core material, RESEARCH OF PYROCARBON with the organic high molecular polymer polyacrylonitrile is the external cladding material of graphite powder particle, conductive doped dose of acetylene black powder in the RESEARCH OF PYROCARBON in the coating process, contain native graphite 90% percetage by weight in this composite graphite negative electrode material, RESEARCH OF PYROCARBON 10% percetage by weight of organic high molecular polymer polyacrylonitrile, the conductive agent acetylene black of being mixed is 1% of native graphite amount, the specific surface of composite graphite negative electrode material is 5 meters squared per gram, its granularity D
50Be 15 μ m.
Its preparation method is, claim the organic high molecular polymer polyacrylonitrile 20 grams, be dissolved in N, in the dinethylformamide, polyacrylonitrile is at N, concentration in the N-dimethylformamide is 100mlN, contain 10 gram polyacrylonitrile in the N-dimethylformamide, be that the 90 gram natural graphite powders of 1～30 μ m and the acetylene black powder of 0.9 gram that particle size range is 0.1～40 μ m place the container that has the condensation retracting device with particle size range again, under 25 ± 1 ℃ temperature, 200 rev/mins mixing speed mixed 5 hours, it is mixed, be warming up to 200 ℃ of evaporates to dryness, stirring-granulating in the evaporate to dryness process is up to the solvent distilled-to-dryness.Mixing speed when the evaporate to dryness stirring-granulating is 700 rev/mins, and the outer surface that is formed on the native graphite powder particles is coated with the native graphite powder particles that one deck contains the organic high molecular polymer polyacrylonitrile of conductive agent acetylene black.In the process of solvent evaporated, the solvent condenses that steams is reclaimed.The outer surface of evaporate to dryness is coated with the crucible that native graphite powder particles that one deck contains the polyacrylonitrile of acetylene black powder places alundum (Al, and to be coated with the thickness of native graphite powder particles that one deck contains the polyacrylonitrile of acetylene black powder be 10cm to the outer surface of evaporate to dryness in the crucible of alundum (Al.In push-plate type or rotatable continuous tunnel furnace, feed the protective gas argon gas; the flow of argon gas is 4000 liters/hour; the alundum (Al crucible of native graphite powder particles that one deck contains the polyacrylonitrile of acetylene black powder that is coated with that fills evaporate to dryness is moved in the heating zone of continuous tunnel furnace; the graphite powder particle that one deck contains the polyacrylonitrile of acetylene black that is coated with of evaporate to dryness is heated up under the protection of protective gas argon gas; programming rate is 10 ℃/minute; rise to 1200 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace; in argon gas atmosphere, carry out high temperature cabonization; the temperature of flat-temperature zone is controlled at 1200 ℃ in the continuous tunnel furnace; it moves after 2 hours in flat-temperature zone in continuous tunnel furnace; move into cooling area again; lower the temperature in the atmosphere of argon gas, reduce to room temperature, the speed of cooling is 15 ℃/minute.Filling in heating zone, flat-temperature zone, cooling area and being coated with the translational speed of alundum (Al crucible of graphite powder particle that one deck contains the polyacrylonitrile of acetylene black powder is 10 centimeters/minute.After reducing to room temperature, with product with commercially available with the corundum be the airslide disintegrating mill of crushing chamber inner lining material product is crushed to meso-position radius D50 is 15 μ m, the product of making is made negative pole, get product of the present invention and account for 90% percetage by weight, binding agent PVDF (Kynoar) 10% percetage by weight, mix the furnishing pulpous state, be coated on the two sides of Copper Foil, at air drying, make negative pole, to electrode is the lithium sheet metal, forms test cell, and electrolyte is 1MLiPF
6/ EC+DMC.Its specific capacity reaches 350mAh/g, cycle performance as shown in Figure 1, the transmission electron microscope picture of the shell structure of composite graphite negative electrode material as shown in Figure 2, its efficiency for charge-discharge reaches 85%.
Embodiment 3
Composite graphite negative electrode material for lithium cell in the present embodiment, with the native graphite powder particles is core material, RESEARCH OF PYROCARBON with the organic high molecular polymer Kynoar is the graphite powder particle external cladding material, conductive doped dose of copper powder in the RESEARCH OF PYROCARBON in the coating process, contain native graphite 95% percetage by weight in this composite graphite negative electrode material, RESEARCH OF PYROCARBON 5% percetage by weight of organic high molecular polymer Kynoar, the amount of the conductive agent copper powder that is mixed is 0.5% percetage by weight of natural graphite powder, the specific surface of composite graphite negative electrode material is 4 meters squared per gram, its granularity D
50Be 20 μ m.
Its preparation method is, claim the organic high molecular polymer Kynoar 10 grams, be dissolved in solvent N, in the dinethylformamide, Kynoar is at N, concentration in the N-dimethylformamide is 100mlN, contain 10 gram Kynoar in the N-dimethylformamide, with particle size range be that 95 gram natural graphite powders and the particle size ranges of 1～25 μ m are the copper powder of 0.475 gram of 0.1～15 μ m, place the container that has the condensation retracting device, under 49 ± 1 ℃ temperature, 200 rev/mins mixing speed mixed 4 hours, and it is mixed, and was warming up to 150 ℃ of evaporates to dryness, stirring-granulating in the evaporate to dryness process is up to the solvent distilled-to-dryness.Mixing speed when the evaporate to dryness stirring-granulating is 500 rev/mins, and the outer surface that is formed on the native graphite powder particles is coated with the native graphite powder particles that one deck contains the organic high molecular polymer Kynoar of conductive agent copper powder, in the process of evaporate to dryness the solvent condenses that steams is reclaimed.The outer surface of evaporate to dryness is coated with the crucible that native graphite powder particles that one deck contains the Kynoar of copper powder places alundum (Al, and to be coated with the thickness of native graphite powder particles that one deck contains the Kynoar of copper powder be 5cm to the outer surface of evaporate to dryness in the crucible of alundum (Al.In push-plate type or rotatable continuous tunnel furnace, feed protective gas nitrogen; the flow of nitrogen is 5000 liters/hour; the alundum (Al crucible of native graphite powder particles that one deck contains the Kynoar of copper powder that is coated with that fills evaporate to dryness is moved in the heating zone of continuous tunnel furnace; the graphite powder particle that one deck contains the Kynoar of copper powder that is coated with of evaporate to dryness is heated up under the protective gas protection of nitrogen gas; programming rate is 5 ℃/minute; rise to 1100 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace; in the atmosphere of nitrogen, carry out high temperature cabonization; the temperature of flat-temperature zone is controlled at 1100 ℃ in the continuous tunnel furnace; it moves after 3 hours in flat-temperature zone in continuous tunnel furnace; move into cooling area again; lower the temperature in protective gas nitrogen, reduce to room temperature, the speed of cooling is 10 ℃/minute.Filling in heating zone, flat-temperature zone, cooling area and being coated with the translational speed of alundum (Al crucible of graphite powder particle that one deck contains the Kynoar of copper powder is 5 centimeters/minute.After reducing to room temperature, with product with commercially available be that the airslide disintegrating mill of crushing chamber liner is crushed to meso-position radius D with product with the corundum
50Be 20 μ m.Be made into negative pole, be mounted to battery and test, its specific capacity reaches 360mAh/g, and its efficiency for charge-discharge reaches 88%, and cycle performance as shown in Figure 1.
Embodiment 4
The product of present embodiment and preparation method and embodiment 3 are identical, and only different is that conductive agent is a silver powder, and its specific capacity is 370mAh/g, and efficiency for charge-discharge is 90%.
Embodiment 5
Composite graphite negative electrode material for lithium cell in the present embodiment, with the electrographite particle is core material, RESEARCH OF PYROCARBON with epoxy resin is the external cladding material of artificial graphite powder particle, conductive doped dose of commercially available silver powder in the RESEARCH OF PYROCARBON in the coating process, contain electrographite 60% percetage by weight in this composite graphite negative electrode material, RESEARCH OF PYROCARBON 40% percetage by weight of epoxy resin, the amount of the conductive agent silver powder that is mixed is 5% of an artificial quantity of graphite, the specific surface of composite graphite negative electrode material is 6 meters squared per gram, its granularity D
50Be 5 μ m.
Its preparation method is, claim epoxy resin 81 grams, be dissolved in the solvent acetone, the concentration of epoxy resin in acetone is to contain 20 gram epoxy resin in the 100ml acetone, with particle size range be that 60 gram electrographite powder and the particle size ranges of 0.1～80 μ m are the silver powder of 0.1～50 μ m, place the container that has the condensation retracting device, under 11 ± 1 ℃ temperature, 20 rev/mins mixing speed mixed 22 hours, it is mixed, be warming up to 65 ℃ of evaporates to dryness, stirring-granulating in the evaporate to dryness process is up to the solvent distilled-to-dryness.Mixing speed when the evaporate to dryness stirring-granulating is 2000 rev/mins, and the outer surface that is formed on the electrographite powder is coated with the electrographite powder particles that one deck contains the epoxy resin of conductive agent silver powder.In the process of evaporate to dryness, the solvent condenses that steams is reclaimed.The outer surface of evaporate to dryness is coated with the electrographite powder particles that one deck contains the epoxy resin of silver powder places silica crucible, to be coated with the thickness of electrographite powder particles that one deck contains the epoxy resin of silver powder be 10cm to the outer surface of evaporate to dryness in silica crucible.In push-plate type or rotatable continuous tunnel furnace, feed the protective gas argon gas; the flow of argon gas is 10000 liters/hour; the silica crucible of electrographite powder particles that one deck contains the epoxy resin of silver powder that is coated with that fills evaporate to dryness is moved in the heating zone of continuous tunnel furnace; the electrographite powder particles that one deck contains the epoxy resin of silver powder that is coated with of evaporate to dryness is heated up under the protection of protective gas argon gas; programming rate is 25 ℃/minute; rise to 1500 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace, in the atmosphere of argon gas, carry out high temperature cabonization.The temperature of flat-temperature zone is controlled at 1500 ℃ in the continuous tunnel furnace, and it moves after 1.2 hours in the flat-temperature zone of continuous tunnel furnace, moves into cooling area again, lowers the temperature in the protective gas argon gas, reduces to room temperature, and the speed of cooling is 50 ℃/minute.Filling in heating zone, flat-temperature zone, cooling area and being coated with the translational speed of silica crucible of graphite powder particle that one deck contains the epoxy resin of silver powder is 10 centimeters/minute, reducing to room temperature, is that the airslide disintegrating mill of crushing chamber liner is meso-position radius D with the product pulverizing in order to corundum
50Be 5 μ m.
Embodiment 6
The composite graphite negative electrode material that the lithium ion battery of present embodiment is used, basic identical with embodiment 5, only different is with the RESEARCH OF PYROCARBON of polyvinyl chloride is the external cladding material of artificial graphite powder, and conductive agent is commercially available silver palladium alloy powder, specific surface 5 meters squared per gram of composite graphite negative electrode material.
Its preparation method is substantially with embodiment 5, and only different is to claim polyvinyl chloride 79 grams, is dissolved in the solvent chloroform, and the concentration of polyvinyl chloride in chloroform is to contain 20 gram polyvinyl chloride in the 100ml chloroform.Under 20 ± 1 ℃ temperature, 1000 rev/mins were stirred 1 hour, and rose to 85 ℃ of evaporates to dryness.Mixing speed is 100 rev/mins in the evaporate to dryness process.To be coated with the thickness of electrographite powder particles that one deck contains the polyvinyl chloride of silver-colored palladium powder be 50cm to the outer surface of evaporate to dryness in the alundum (Al crucible; the flow of protective gas nitrogen is 200 liters/hour; 1 ℃/minute of programming rate; rise to 700 ℃; moved 7 hours in continuous tunnel furnace, cooling rate is 2 ℃/minute.Translational speed in heating zone, flat-temperature zone, cooling area is 0.5 centimeters/minute.
Embodiment 7
The composite graphite negative electrode material for lithium cell of present embodiment is basic identical with embodiment 5, and only different is that the conductive agent electrically conductive graphite is 10% of a native graphite amount, and the specific surface of composite graphite negative electrode material is 4 meters squared per gram, its granularity D
50Be 40 μ m.
Its preparation method is substantially with embodiment 2, and only different is under 30 ± 1 ℃ temperature, and 2000 rev/mins mixing speed stirred 0.6 hour, and it is mixed.In the process of evaporate to dryness; mixing speed is 500 rev/mins; the outer surface of evaporate to dryness is coated with the thickness 1cm of natural graphite powder that one deck contains the polyacrylonitrile of electrically conductive graphite powder in the crucible of alundum (Al; the flow of protective gas nitrogen is 100 liters/hour; rise to 550 ℃; temperature is controlled at 550 ℃ in the flat-temperature zone; moved in the flat-temperature zone of continuous tunnel furnace 10 hours, filling the translational speed of alundum (Al of graphite powder particle that one deck contains the polyacrylonitrile of electrically conductive graphite powder in heating zone, flat-temperature zone is 0.3 centimeters/minute.
Embodiment 8
Composite graphite negative electrode material for lithium cell of present embodiment and preparation method thereof; basic identical with embodiment 3; only different is that the protective gas that feeds in push-plate type or rotatable continuous tunnel furnace is to contain hydrogen in the nitrogen, and the amount of the hydrogen that is added accounts for 2.5% percentage by volume of protective gas.
Embodiment 9
Composite graphite negative electrode material for lithium cell of present embodiment and preparation method thereof is basic identical with embodiment 3; only different is that the protective gas that feeds in push-plate type or rotatable continuous tunnel furnace is to contain carbon monoxide in the nitrogen, and the carbon monoxide that is added accounts for 1.5% percentage by volume of protective gas.
Embodiment 10
Composite graphite negative electrode material for lithium cell of present embodiment and preparation method thereof is basic identical with embodiment 3; the location below 300 ℃ that only different is at heating zone; add oxidizing gas oxygen in the argon gas of the inert gas of protective gas, the amount of the oxygen that is added accounts for 3% percentage by volume of protective gas.
Embodiment 11
Composite graphite negative electrode material for lithium cell of present embodiment and preparation method thereof; basic identical with embodiment 3; the location below 300 ℃ that only different is at heating zone; add the oxidizing gas air in the inert gas argon gas of protective gas, the amount of the air that is added accounts for 10% percentage by volume of protective gas.
Embodiment 12
Composite graphite negative electrode material for lithium cell of present embodiment and preparation method thereof, basic identical with embodiment 3, only different is that used graphite powder particle external cladding material is a pitch.
Claims (28)
1. composite graphite negative electrode material for lithium cell, with the graphite powder particle is core material, RESEARCH OF PYROCARBON with organic high molecular polymer or organic compound is an external cladding material, it is characterized in that, in the coating process in the RESEARCH OF PYROCARBON conductive doped dose, this composite graphite negative electrode material contains graphite 50-99% percetage by weight, the RESEARCH OF PYROCARBON 1-50% percetage by weight of organic high molecular polymer or organic compound, the conductive agent that is mixed is the 0.01-10% of graphite weight, and the specific surface of composite graphite negative electrode material is 0.1～20 meters squared per gram.
2. according to a kind of composite graphite negative electrode material for lithium cell of claim 1, it is characterized in that said conductive agent copper powder, silver powder, bronze, alloyed powder, carbon black, electrically conductive graphite, aquadag, acetylene black powder one or more powder wherein.
3. according to a kind of composite graphite negative electrode material for lithium cell of claim 1, it is characterized in that alloyed powder is yellow gold powder, silver palladium alloy powder.
4. according to a kind of composite graphite negative electrode material for lithium cell of claim 1, it is characterized in that its specific surface is 0.5～10 meters squared per gram.
5. according to a kind of composite graphite negative electrode material for lithium cell of claim 1, it is characterized in that its granularity D
50Be 0.5-50 μ m.
6. the preparation method of a composite graphite negative electrode material for lithium cell is characterized in that,
1) organic high molecular polymer or organic compound are dissolved with corresponding solvent,,, place the container that has the condensation retracting device, mixed 0.5-24 hour by required amount again with the conductive agent powder of graphite powder and doping,
2) elevated temperature is the solvent distilled-to-dryness, stirring-granulating in the process of solvent evaporated, and the outer surface that is formed on graphite powder particle is coated with one deck and contains the organic high molecular polymer of conductive agent or the graphite powder particle of organic compound,
3) outer surface of evaporate to dryness is coated with one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound places resistant to elevated temperatures container,
4) in push-plate type or rotatable continuous tunnel furnace, feed protective gas, make to fill to be coated with the high-temperature resistant container that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent or organic compound and to move in the heating zone of push-plate type or rotatable continuous tunnel furnace,
5) make be coated with that one deck contains the organic high molecular polymer of conductive agent powder or the graphite powder particle of organic compound heats up under the protection of protective atmosphere; rise to 500-1500 ℃; again it is moved in the flat-temperature zone of continuous tunnel furnace; under the protection of protective atmosphere; carry out high temperature cabonization in the flat-temperature zone of continuous tunnel furnace, the temperature of flat-temperature zone is controlled at 500-1500 ℃ in the continuous tunnel furnace, in its flat-temperature zone in continuous tunnel furnace after mobile 0.1-10 hour; move into cooling area
6) protection of protective atmosphere drops to room temperature.
7. according to the preparation method of a kind of composite graphite negative electrode material for lithium cell of claim 6, it is characterized in that, said organic high molecular polymer is wherein a kind of of phenol-formaldehyde resin modified, epoxy resin, polyacrylonitrile, polystyrene, Vingon, Kynoar, polyvinyl alcohol, poly furfuryl alcohol, phenol formaldehyde resin, and organic compound is wherein a kind of of coal tar, pitch.
8. according to the preparation method of a kind of composite graphite negative electrode material for lithium cell of claim 7, it is characterized in that, the solvent that is used to dissolve organic high molecular polymer or organic compound is acetone, toluene, dimethylbenzene, chlorobenzene, oxolane, butyl acetate, N, dinethylformamide, N-methyl pyrrolidone, chloroform and derivative thereof, water.
9. the preparation method of a kind of composite graphite negative electrode material for lithium cell according to Claim 8, it is characterized in that organic high molecular polymer or the organic compound concentration in solvent is to contain 1～200 gram organic high molecular polymer or organic compound in 100 milliliters of solvents.
10. according to the preparation method of a kind of composite graphite negative electrode material for lithium cell of claim 6, it is characterized in that raw materials used graphite is electrographite or native graphite, its granularity is 0.1-100 μ m.
11. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 10 is characterized in that its raw material graphite particle size is 1-40 μ m.
12. preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6, it is characterized in that used conductive agent powder is copper powder, silver powder, bronze, alloyed powder, carbon black, electrically conductive graphite, aquadag, acetylene black powder one or more powder wherein.
13. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 12 is characterized in that its conductive agent granularity is 0.01-50 μ m.
14. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that, under 10-50 ℃ temperature, with 1-5000 rev/min mixing speed, mixes 0.1-24 hour in the container that has the condensation retracting device.
15. preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6, it is characterized in that, elevated temperature is to 51-200 ℃, stirring-granulating in the evaporate to dryness process, until the organic high molecular polymer that will dissolve or the solvent distilled-to-dryness of organic compound, the mixing speed during its stirring-granulating is 1-5000 rev/min.
16. preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6, it is characterized in that to be coated with the thickness that one deck contains the graphite powder particle of the organic high molecular polymer of conductive agent powder or organic compound be 0.1-50 centimetre to the outer surface of evaporate to dryness in resistant to elevated temperatures container.
17. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 16 is characterized in that the thickness of graphite powder particle is 1-10 centimetre.
18. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that, said protective gas is to add an amount of reducibility gas in inert gas or the inert gas.
19. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 18 is characterized in that, inert gas is wherein a kind of of nitrogen, argon gas, helium.
20. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 18 is characterized in that reducibility gas is hydrogen or carbon monoxide, the hydrogen that is added or the amount of carbon monoxide are the 0.1-50% percentage by volume of protective gas.
21. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 18 is characterized in that, protective gas feed flow in push-plate type or the rotatable continuous tunnel furnace be the 10-10000 liter/hour.
22. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 21 is characterized in that, its flow be the 100-5000 liter/hour.
23. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that heat up, programming rate is 0.1～25 ℃/minute under protective atmosphere.
24. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that move into cooling area, cooling rate is 0.5～50 ℃/minute.
25. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that, is 0.1～50 centimeters/minute in the translational speed of heating zone, flat-temperature zone, cooling area high-temperature crucible.
26. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6 is characterized in that, product is crushed to D
50Be 0.5-50 μ m.
27. the preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 26 is characterized in that D
50Be 1-25 μ m.
28. preparation method according to a kind of composite graphite negative electrode material for lithium cell of claim 6; it is characterized in that; the low-temperature zone below 300 ℃ at heating zone adds oxidizing gas oxygen or air in inert gas, the oxygen that is added or the amount of air are the 0.1-50% percentage by volume of protective gas.
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| CNB991262158A CN1171333C (en) | 1999-12-15 | 1999-12-15 | Composite graphite negative electrode material for lithium cell and its preparation method |
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