CN102867945B - Preparation method of graphite negative electrode material containing hollow carbon nanostructure for lithium ion battery - Google Patents
Preparation method of graphite negative electrode material containing hollow carbon nanostructure for lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphite negative electrode material containing a hollow carbon nanostructure for a lithium ion battery. The preparation method comprises the following steps of: firstly adopting an explosion method to prepare asphalt doped with nano-metal particles, crushing the asphalt doped with the nano-metal particles to obtain powdered asphalt with the particle size of 60-300 meshes, adopting the powdered asphalt as a binding agent, taking natural graphite as aggregate, uniformly mixing the two by adopting a ball milling way or a mechanical stirring method, and adopting a hot-pressing sintering method to obtain the graphite negative electrode material containing the hollow carbon nanostructure for the lithium ion battery. A catalyst disclosed by the invention has the advantages of high lithium storage capacity, high coulombic efficiency, good cycle performance, excellent rate capability and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of negative electrode for lithium ion battery material, particularly relate to a kind of preparation method of the graphite negative material of lithium ion battery that contains hollow carbon nanostructure.
Background technology
Lithium ion battery is with its high-energy-density, long circulation life, the advantages such as memory-less effect at electronic product as mobile phone, video camera, notebook computer lamp field is universal rapidly, and at electric tool, electric bicycle, the aspects such as electric automobile obtain certain progress.But along with social development, people have higher requirement and expectation to lithium ion battery, wish that capacity is larger, coulomb efficiency is higher, and high rate performance is better, and the life-span is longer etc.The raising of battery performance depends on the development and improvement of electrode material.Therefore for a long time, improve the specific capacity of lithium ion battery negative material, reduce irreversible capacity first, improve a coulomb efficiency, improve high rate performance, improve circulation safe performance, be the emphasis of negative material research always.
In all lithium ion battery negative materials, native graphite has lower discharge platform, and it is with low cost, aboundresources.But its structure is layer structure, easily cause the common insertion of solvent molecule, its synusia in charge and discharge process is peeled off, cause cycle performance of battery poor, poor safety performance.The modified natural graphite that adopts different method of modifying to obtain on native graphite basis improves a lot in solvent compatibility and circulation safe performance, is the product of occupation rate maximum in the market.Main modified method has at present, spheroidization processing, and oxidation modification, fluorinated modified, chemical surface treatment, surface is coated etc.Because the layer structure of graphite own limits, theoretical capacity only has 372mAh/g, though through modification, still can not meet following needs.The solvent compatibility of Delanium is good, and circulation and high rate performance are better, but because its specific capacity does not have large increase, and its preparation cost is higher, does not have great advantage, and the occupation rate on market is not high.As the modifying natural graphite product of Shenzhen Bei Terui, after being processed, natural flake graphite spheroidization carries out the coated processing of carbon, coulomb efficiency first of acquisition 93% and the discharge capacity of 365 mAh/g.(" research of modified spherical natural graphite lithium ionic cell cathode material ", kingdom's equality, 2005 years the 13 volumes, the 3rd phase, 24 9～2 53 synthetic chemistries) negative material prepared of the amorphous carbon coated natural graphite mentioned of CN 101117911 A, efficiency is more than 92% first, discharge capacity is 355 mAh/g first, the specific capacity of the artificial graphite microspheres of Shanghai China fir Taxodiaceae skill (seeing the negative pole brief introduction of selling in the company's site of its Shanghai China fir Taxodiaceae skill) also only has 280-350mAh/g, cannot break through theoretical capacity, visible want obtain the higher not single modification of capacity just can accomplish.
And other the Novel anode material that has high theoretical treatment capacity is as silicon, tin, metal oxides etc., in removal lithium embedded process, have larger volumetric expansion, make its cycle performance mostly not good, and technique etc. is immature at present, have limited their commercial applications.
How to obtain lithium storage content high, coulomb efficiency is high, good cycle, and the good negative material of high rate performance is one of key improving performance of lithium ion battery, and whether cost is cheap, whether technique simple becomes the criterion that material whether can large-scale commercial application.At present, also do not have material better to meet the following demand to heavy-duty battery.
Summary of the invention
The object of this invention is to provide a kind of lithium storage content high, coulomb efficiency is high, good cycle, and high rate performance is good, the preparation method of the graphite negative material of lithium ion battery that what cost was low contain hollow carbon nanostructure.
The technical solution adopted in the present invention is: adopt the pitch of metal nanoparticle doping to make binding agent, powdered graphite does aggregate, adopt the method for hot pressed sintering, a step completes bitumencarb coated graphite carbonized graphiteization and a large amount of hollow carbon nanostructure original position and forms.
The concrete preparation method of the present invention is as follows:
(1) what, first adopt is that explosion method is prepared nano-metal particle doping pitch: adopt tar as the raw material of preparing pitch, in tar, add in mass ratio inorganic salts or organic salt and the burster (having the small-molecule substance of low decomposition temperature) of transition metal, in modulation pitch in temperature-rise period, burster reaches decomposition temperature and produces slight blast, make that slaine is more dispersed to be opened, continue afterwards to heat up, be finally modulated into the pitch that is dispersed with nano-metal particle.Concrete preparation method is shown in " preparation of nano nickle granules doping pitch fibers ", lijin, Guo Quangui etc., " carbon " (Carbon) 2012 years, 50 volumes, 5 phase 2045-2047. (Li, Jin, Guo, Quangui, Shi, Jingli, Gao, Xiaoqing, Feng, Zhihai, Fan, Zhen, Liu, Lang, Preparation of Ni nanoparticle-doped carbon fibers Carbon, 2012,50,5,2045-2047)
(2), step (1) obtains the pitch of nano-metal particle through fragmentation, grinds, and obtains particle diameter and is the Powdered pitch of 60 ~ 300 order, for subsequent use;
(3), adopt Powdered pitch to make binding agent, average grain diameter is that the native graphite of 5-30 μ m does aggregate, the consumption of binding agent accounts for the 20%-70% of gross mass, adopts ball milling method or mechanical agitation method to mix the two;
(4), adopt the method for hot pressed sintering, be protective gas at inert gas or carbon dioxide, processing pressure is 1-50Mpa, heat treatment mode is: keep pressure, with the programming rate of 2-4 DEG C/min, be warming up to 2000-3000 DEG C, constant temp. heating is processed 1-10h, then be naturally down to room temperature, obtaining block product is electrode material activity material; In this heat treatment process, the metallic particles volatilization of can gasifying does not gradually have or only has a small amount of remnants to product;
(5) block product is processed into average grain diameter at 5-30 μ m active matter powder, obtains the graphite negative material of lithium ion battery that contains hollow carbon nanostructure.
The described tar of step of the present invention (1) can be selected petroleum residual oil, coal tar, and ethylene bottom oil, heavy oil etc. contain one or more in the chemical products of condensed-nuclei aromatics.
The described transition metal of step of the present invention (1) is iron, cobalt or nickel, and the inorganic salts of transition metal are transition metal nitrate.The organic salt of transition metal is oxalates, acetate or transient metal complex.
In the pitch of nano-metal particle prepared by step of the present invention (1), the form of nano-metal particle is metal simple-substance or the metal oxide of nano-scale particle size.Its particle diameter is distributed in 5-100 nm, and average grain diameter is at 10-50 nm.
In the pitch of nano-metal particle prepared by step of the present invention (1), nano-metal particle accounts for the 0.1-30% of asphalt quality.
Native graphite of the present invention is one or more of the graphite forms such as natural flake graphite, graphite microcrystal or spherical natural graphite, and average grain diameter is 5-30 μ m.
Inert gas of the present invention is nitrogen, argon gas or helium.
The artificial graphite cathode material for lithium ion batteries that the present invention makes is made up of three kinds of components, comprises the graphitic composition as aggregate, as the bitumencarb component of coating layer and binding agent and the carbon lar nanometric cavities part of One's name is legion.
The a large amount of carbon lar nanometric cavities structure containing in the artificial graphite cathode material for lithium ion batteries that the present invention makes is the hollow structure of class onion fullerene.Be irregular polygonized structure, contain multi-layer graphene lamella.
The artificial graphite cathode material for lithium ion batteries of preparing taking the present invention is raw material, according to the general preparation method of button cell, active matter powder, conductive agent, binding agent are pressed to certain mass than mixing, add in n-methlpyrrolidone, ultrasonic dispersion magnetic agitation mixing makes cathode size, coats on Copper Foil, and cut-parts are as negative plate after drying, be assembled into battery, carry out constant current charge-discharge test.(concrete seeing " lithium ion simulated battery ", lithium electricity information, 2010, the 31 phase supplementary issues.）
The present invention compared with prior art tool has the following advantages,
Because adopting bitumencarb coated graphite and carrying out carbonized graphite processing, this Delanium has the solvent compatibility of common Delanium good, and coulomb efficiency is high, the advantage of good cycle.The artificial plumbago negative pole material surface of this hollow carbon nanostructure that contains a large amount of original positions formation is made up of graphited bitumencarb, there is the character of soft carbon, with propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) equal solvent compatibility is good, form stable solid electrolyte (SEI) film, avoid occurring that propene carbonate embeds the phenomenon that native graphite interlayer causes native graphite layer to peel off, make material there is good cyclical stability, longer useful life.The efficiency first of this negative material is more than 80%, and coulomb efficiency is afterwards mostly more than 99%.Prepare nano-metal particle in the raw material of this artificial plumbago negative pole material is dispersed in raw material simultaneously more uniformly, in heat treatment process, can there is the final original position Formed of a series of variation lar nanometric cavities structure, this structure provides a large amount of storage lithium spaces and active sites, the lithium storage content of material has had significantly raising, reaches the capacity of the current most of business-like graphite cathode material of 520 mAh/g(within the scope of 280-360 mAh/g.) simultaneously the high rate performance of material also because the existence of a large amount of hollow carbon nanostructures is greatly improved, under the high current density of 1000 mA/g, still can reach 100-300 mAh/g.Can be used for common lithium ion battery and power lithium-ion battery, and raw material sources are abundant, with low cost, manufacture craft is simple, is easy to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the cross-sectional view of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1.In figure, 1 is graphitization bitumencarb; 2 carbon lar nanometric cavities structures; The 3rd, native graphite.
Fig. 2 is the preparation flow schematic diagram of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1
Fig. 3 is the transmission electron microscope collection of illustrative plates of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1
Fig. 4 is: the X-S x ray diffraction collection of illustrative plates of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1
Fig. 5 is the first charge-discharge curve of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1, and current density is 50 mA/g.
Fig. 6 is that in the embodiment of the present invention 1 and comparative example 1, product is as the first charge-discharge curve of negative material, and current density is 50 mA/g.
Fig. 7 is that in comparative example 2 of the present invention, natural flake graphite is as the first charge-discharge curve of negative material, and current density is 50 mA/g.
Fig. 8 is the cycle performance of the man-made graphite cathode material for lithium ion battery of the embodiment of the present invention 1.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, the lithium ion battery negative material and the preparation method that the present invention are proposed below in conjunction with accompanying drawing, lithium ion battery carries out detailed description.
Embodiment 1: adopt ethylene bottom oil as the raw material of preparing pitch, in tar, add in mass ratio nickel nitrate and picric acid (burster) (in 100g ethylene bottom oil, adding 5g nickel nitrate and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, in temperature-rise period, nickel nitrate decomposes (110 DEG C start to decompose), continue afterwards to heat up, picric acid reaches decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that nickel oxide is more dispersed to be opened, temperature rises to 420 DEG C, continue stir about 0.5 hour, stop, finally be modulated into and there is the pitch that nano metal nickel uniform particles is disperseed.Metal quality mark in its medium pitch is 10%, grinds 100 mesh standard sieves after pulverizing, for subsequent use.Selecting natural flake graphite is graphite source, and wet ball grinding is crossed 100 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 20:80 take material, adopt the mode of ball milling to mix, rotating speed is 200r/min, the time is 2 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 2 DEG C/min to 2750 DEG C of programming rate, 2750 DEG C of constant temperature times are 2 hours, pressure is that 25MPa. is after naturally cooling, take out block product, be processed into powder, cross 100 mesh sieves, obtain Delanium sample powder, for subsequent use.
The present invention's half-cell method of testing used is: make CR2016 type button cell, Delanium sample powder, the 1-METHYLPYRROLIDONE that contains 10% Kynoar and 10% black the mixing of conductive acetylene, be applied on Copper Foil, put into vacuum drying chamber, for subsequent use 120 DEG C of vacuumizes 10 hours, simulated battery is assemblied in the upper dried shrimps Kai Luona glove box that is full of argon gas and carries out, and electrolyte is 1M LiPF
6+ EC:DMC=1:1 (mass ratio), adopting metal lithium sheet is to electrode.Chemical property carries out on the blue electric CT2001A type battery test system in Wuhan, discharges and recharges system: current density is 50 mA/g or 100mA/g, constant current charge-discharge, and voltage range is 0.005-3.000v.
Comparative example 1, this routine pitch does not have metal nanoparticle doping.Other steps are with embodiment 1, and first charge-discharge curve is referring to Fig. 6.
Comparative example 2, selects natural flake graphite to replace Delanium as lithium ion battery negative material, and part of detecting is with embodiment 1.
Fig. 1 is the structure diagram of the artificial graphite cathode material for lithium ion batteries that proposes of the present invention, this lithium ion battery negative material comprises three kinds of components of combining closely, bitumencarb is tightly wrapped in native graphite, is again the matrix with the carbon lar nanometric cavities structure of class onion fullerene simultaneously.Three kinds of components are being brought into play and are being acted synergistically in the combination property that improves material.
In the present embodiment, carbon lar nanometric cavities structure is that original position generates.Carbon lar nanometric cavities number of structures is numerous and be dispersed in more uniformly in whole material, for storage and the transfer of lithium ion provide space and path, remarkable for the raising effect of material lithium storage content and high rate performance.
Fig. 3 is the transmission electron microscope picture of man-made graphite cathode material for lithium ion battery in the present embodiment 1, therefrom can be clearly seen that and in material, has the carbon lar nanometric cavities structure of a large amount of class onion fullerenes to exist, particle diameter distribution uniform.Be polygon, class onion fullerene structure, center is cavity.They are embedded in bitumencarb, and graphitic composition is closely connected, and are conducive to storage and the transfer of lithium ion.The raising of the chemical property to material plays an important role.
Fig. 4 is the XRD collection of illustrative plates of man-made graphite cathode material for lithium ion battery in the present embodiment 1.1 line represents the XRD collection of illustrative plates of the asphalt sample of the doping metals particle of 1000 DEG C of processing, and 2 lines represent the XRD collection of illustrative plates of the sample products of 2750 DEG C of processing, therefrom can find out that the degree of graphitization of material raises and increases with temperature, and the content of nickel reduces.In final product, almost do not have.
Fig. 5 is the first charge-discharge curve of this product in the present embodiment 1, and current density is identical, is 50mA/g.
Fig. 6 is the first charge-discharge curve of product and comparative example's 1 product in embodiment 1, and current density is identical, is 50 mA/g.As shown in Figure 6, the excellent product performance of being prepared with the pitch of doping metals particle by method provided by the invention, specific capacity is higher.
Fig. 7 for comparative example 2(negative material be natural flake graphite) in the first charge-discharge curve of this product, current density is identical, is 50mA/g.
According to Fig. 5, Fig. 7, contrasts two groups of charging and discharging curves known, and the capacity of the artificial plumbago negative pole material of preparing by preparation method of the present invention is greater than the capacity of natural flake graphite, is also greater than the theoretical capacity of graphite: 372 mAh/g.Coulomb efficiency first of the artificial plumbago negative pole material of simultaneously preparing by preparation method of the present invention is also apparently higher than coulomb efficiency first of natural flake graphite material.
Fig. 8 is the cyclic curve of man-made graphite cathode material for lithium ion battery in the present embodiment 1, front 5 circulations are carried out under 50mA/g, later circulation is to carry out under 100mA/g, under 100mA/g, circulate still can be in 440mAh/g left and right, apparently higher than current business-like graphite products for the capacity of this product as can be seen here.
Table 1 is embodiment 1-6, the tap density of comparative example 1-2 and Electrochemical results.
Embodiment 2, adopt coal tar as the raw material of preparing pitch, in coal tar, add in mass ratio nickel nitrate and picric acid (burster) (in 100g coal tar, adding 1g nickel nitrate and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, in temperature-rise period, nickel nitrate decomposition (75 DEG C start to decompose) obtains nickel oxide, continue afterwards to heat up, picric acid reaches decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that nickel oxide is more dispersed to be opened, temperature rises to 420 DEG C, continue stir about 0.5 hour, stop, finally be modulated into and there is the pitch that nano metal nickel uniform particles is disperseed.Metal quality mark in its medium pitch is 1%, grinds 300 mesh standard sieves after pulverizing, for subsequent use.Selecting natural flake graphite is graphite source, and wet ball grinding is crossed 300 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 50:50 take material, adopt the mode of ball milling to mix, rotating speed is 200r/min, the time is 2 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 2 DEG C/min to 3000 DEG C of programming rate, the time is 1 hour, pressure is that 10MPa. is after naturally cooling, take out block product, be processed into powder, cross 300 mesh sieves, obtain Delanium sample powder, for subsequent use.Other steps are with embodiment 1.During as lithium ion battery negative, chemical property is similar to embodiment 1.Test result is in table 1.
Embodiment 3,
Adopt petroleum residual oil as the raw material of preparing pitch, in petroleum residual oil, add in mass ratio ferric nitrate and picric acid (burster) (in 100g coal tar, adding 30g ferric nitrate and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, in temperature-rise period, ferric nitrate divides and solves iron oxide, continue afterwards to heat up, picric acid reaches decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that iron oxide is more dispersed to be opened, temperature rises to 420 DEG C, continue stir about 0.5 hour, stop, being finally modulated into and thering is the pitch that nanometer metallic iron uniform particles is disperseed.Metal quality mark in its medium pitch is 20%, grinds 300 mesh standard sieves after pulverizing, for subsequent use.Selecting graphite microcrystal is graphite source, and wet ball grinding is crossed 200 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 30:70 take material, adopt the mode of ball milling to mix, rotating speed is 200r/min, the time is 5 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 2 DEG C/min to 2500 DEG C of programming rate, the time is 3 hours, pressure is that 50MPa. is after naturally cooling, take out block product, be processed into powder, cross 300 mesh sieves, obtain Delanium sample powder, for subsequent use.Other steps are with embodiment 1.During as lithium ion battery negative, chemical property is similar to embodiment 1.Test result is in table 1.
Embodiment 4
Adopt heavy oil as the raw material of preparing pitch, in heavy oil, add in mass ratio cobalt oxalate and picric acid (burster) (in 100g heavy oil, adding 15g cobalt oxalate and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, temperature-rise period mesoxalic acid cobalt decomposes, continue afterwards to heat up, picric acid reaches decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that cobalt oxide is more dispersed to be opened, temperature rises to 420 DEG C, continue stir about 0.5 hour, stop, being finally modulated into and thering is the homodisperse pitch of nano metal cobalt granule.Metal quality mark in its medium pitch is 30%, grinds 100 mesh standard sieves after pulverizing, for subsequent use.Selecting natural flake graphite is graphite source, and wet ball grinding is crossed 100 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 30:70 take material, adopt the mode of ball milling to mix, rotating speed is 200r/min, the time is 2 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 3 DEG C/min to 2750 DEG C of programming rate, the time is 7 hours, pressure is that 15MPa. is after naturally cooling, take out block product, be processed into powder, cross 100 mesh sieves, obtain Delanium sample powder, for subsequent use.Other steps are with embodiment 1.During as lithium ion battery negative, chemical property is similar to embodiment 1.Test result is in table 1.
Embodiment 5
Adopt ethylene bottom oil as the raw material of preparing pitch, in ethylene bottom oil, add in mass ratio ferrocene and picric acid (burster) (in 100g ethylene bottom oil, adding 15g ferrocene and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, intensification reaches picric acid decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that ferrocene is more dispersed to be opened, temperature rises to 420 DEG C, continue stir about 0.5 hour, stop, being finally modulated into and thering is the pitch that nanometer metallic iron uniform particles is disperseed.Metal quality mark in its medium pitch is 10%, grinds 100 mesh standard sieves after pulverizing, for subsequent use.Selecting spherical graphite is graphite source, and wet ball grinding is crossed 100 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 30:70 take material, adopt churned mechanically mode to mix, rotating speed is 200r/min, the time is 2 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 3 DEG C/min to 2550 DEG C of programming rate, the time is 10 hours, pressure is that 20MPa. is after naturally cooling, take out block product, be processed into powder, cross 100 mesh sieves, obtain Delanium sample powder, for subsequent use.Other steps are with embodiment 1.During as lithium ion battery negative, chemical property is similar to embodiment 1.Test result is in table 1.
Embodiment 6
Adopt ethylene bottom oil as the raw material of preparing pitch, in ethylene bottom oil, add in mass ratio nickel nitrate and picric acid (burster) (in 100g ethylene bottom oil, adding 15g nickel nitrate and 5g picric acid), in modulation pitch, in temperature-rise period, constantly stir, intensification reaches picric acid decomposition temperature (approximately 300 DEG C) and produces slightly blast, make that nickel nitrate is more dispersed to be opened, temperature rises to 420 DEG C, continues stir about 0.5 hour, stop, being finally modulated into and thering is the homodisperse pitch of nano nickle granules.Metal quality mark in its medium pitch is 15%, grinds 100 mesh standard sieves after pulverizing, for subsequent use.Selecting spherical graphite is graphite source, and wet ball grinding is crossed 300 mesh standard sieves, for subsequent use.By the pitch sieving and powdered graphite in mass ratio 40:60 take material, adopt churned mechanically mode to mix, rotating speed is 200r/min, the time is 2 hours.After taking out mixture, pack in graphite jig, compacting, is placed in hot press, adopt the mode of high temperature hot pressing sintering to prepare Delanium product, keep pressure, approximately 3 DEG C/min to 2750 DEG C of programming rate, the time is 3 hours, pressure is that 30MPa. is after naturally cooling, take out block product, be processed into powder, cross 100 mesh sieves, obtain Delanium sample powder, for subsequent use.Other steps are with embodiment 1.During as lithium ion battery negative, chemical property is similar to embodiment 1.Test result is in table 1.
Table 1
Claims (10)
1. contain a preparation method for the graphite negative material of lithium ion battery of hollow carbon nanostructure, it is characterized in that comprising following rapid:
(1) what, first adopt is that explosion method is prepared nano-metal particle doping pitch: adopt tar as the raw material of preparing pitch, in tar, add in mass ratio inorganic salts or organic salt and the burster (having the small-molecule substance of low decomposition temperature) of transition metal, in modulation pitch in temperature-rise period, burster reaches decomposition temperature and produces slight blast, make that slaine is more dispersed to be opened, continue afterwards to heat up, be finally modulated into the pitch that is dispersed with nano-metal particle;
(2), step (1) obtains the pitch of nano-metal particle through fragmentation, grinds, and obtains particle diameter and is the Powdered pitch of 60-300 order, for subsequent use;
(3), adopt Powdered pitch to make binding agent, average grain diameter is that the native graphite of 5-30 μ m does aggregate, the consumption of binding agent accounts for the 20%-70% of gross mass, adopts ball milling method or mechanical agitation method to mix the two;
(4), adopt the method for hot pressed sintering, be protective gas at inert gas or carbon dioxide, processing pressure is 1-50Mpa, heat treatment mode is: keep pressure, with the programming rate of 2-4 DEG C/min, be warming up to 2000-3000 DEG C, constant temp. heating is processed 1-10h, then be naturally down to room temperature, obtaining block product is electrode material activity material;
(5) block product is processed into average grain diameter at 5-30 μ m active matter powder, obtains the graphite negative material of lithium ion battery that contains hollow carbon nanostructure.
2. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that the described tar of step (1) is petroleum residual oil, coal tar, ethylene bottom oil, heavy oil containing one or more in the chemical products of condensed-nuclei aromatics.
3. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that the described transition metal of step (1) is iron, cobalt or nickel.
4. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that the inorganic salts of the described transition metal of step (1) are transition metal nitrate.
5. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that the organic salt of the described transition metal of step (1) is oxalates, acetate or transient metal complex.
6. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, it is characterized in that in the pitch of nano-metal particle prepared by step (1), the form of nano-metal particle is metal simple-substance or the metal oxide of nano-scale particle size, its particle diameter is distributed in 5-100 nm, and average grain diameter is at 10-50 nm.
7. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that in the pitch of nano-metal particle prepared by step (1), nano-metal particle accounts for the 0.1-30% of asphalt quality.
8. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, it is characterized in that described native graphite is one or more of natural flake graphite, graphite microcrystal or spherical natural graphite graphite form, average grain diameter is 5-30 μ m.
9. the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure as claimed in claim 1, is characterized in that described inert gas is nitrogen, argon gas or helium.
10. a graphite negative material of lithium ion battery that contains hollow carbon nanostructure, it is characterized in that the artificial graphite cathode material for lithium ion batteries that the preparation method of a kind of graphite negative material of lithium ion battery that contains hollow carbon nanostructure described in claim 1-9 any one makes, it is by the graphitic composition as aggregate, as bitumencarb component and three kinds of component compositions of carbon lar nanometric cavities part of coating layer and binding agent, carbon lar nanometric cavities structure is the hollow structure of class onion fullerene, be irregular polygonized structure, contain multi-layer graphene lamella.
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| CN103811718B (en) * | 2014-02-20 | 2016-08-17 | 深圳市贝特瑞新能源材料股份有限公司 | The preparation method of a kind of graphene-based composite negative pole material and prepared negative material and lithium ion battery |
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