CN103219511A - Ferroferric oxide/carbon composite material with tubular core-shell structure as well as preparation method and application thereof - Google Patents
Ferroferric oxide/carbon composite material with tubular core-shell structure as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ferroferric oxide/carbon composite material with a tubular core-shell structure as well as a preparation method and the application of the ferroferric oxide/carbon composite material. The ferroferric oxide/carbon composite material consists of a ferroferric oxide nanotube and a carbon layer covered on the ferroferric oxide nanotube, and has the tubular core-shell structure which takes the ferroferric oxide nanotube as the core and the carbon layer as the shell. The ferroferric oxide in the composite material has the tubular structure, and the carbon layer has the functions of electric conduction and buffer, so that the cycling stability of the ferroferric oxide can be effectively improved in the charge-discharge process, and the composite material can be used as lithium ion battery cathode material. The preparation method of the ferroferric oxide/carbon composite material with the tubular core-shell structure has the advantages of being simple in technology, low in cost, short in period, low in energy consumption and the like, thus being suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the lithium ion battery field of compound material, be specifically related to tri-iron tetroxide/carbon composite of a kind of tubulose nucleocapsid structure and its production and application.
Background technology
Lithium ion battery has advantages such as operating voltage height, energy density is big, security performance is good, therefore in portable type electronic products such as digital camera, mobile phone and notebook computer, be used widely, also have application prospect for electric bicycle and electric automobile.Present commercial lithium ion battery generally adopts the carbon back negative material, and as graphite, though this material stability is higher, theoretical capacity only has 372mAhg
-1
Compare with material with carbon element, some transition metal oxide has the high theoretical capacity, as Fe
3O
4Theoretical capacity up to 925mAhg
-1This class transition metal oxide (M '
xO
y) general character is arranged: reversible reaction can take place with lithium metal in contained oxygen, and this reaction provides reversible capacity, and the transition metal of embedding lithium formation first (M ') discord lithium generation alloying/take off alloying reaction, its process is:
M’
xO
y+2y?Li→x?M’+y?Li
2O
Though this reaction can provide higher capacity,, cause the rapid decay of capacity because change in volume is bigger in the removal lithium embedded process.At present, effectively slow down capacity fast the method for decay generally be transition metal oxide and other basis material to be carried out compound, comparatively ideal basis material is a material with carbon element.And deposit one deck carbon film by vapour deposition process in oxide particle surface is a kind of simple and easy to do complex method, can prepare oxide/carbon composite on a large scale.
Existing a lot of as the report that basis material prepares composite material in the prior art with carbon, as disclosing a kind of Fe of hollow ball structure among the Chinese patent application CN201110127573.7
3O
4/ C nano particle.This hollow ball adopts a step hydro-thermal or solvent thermal preparation, uses molysite, mineralizer, solvent, surfactant to react 6 hours～96 hours down at 180 ℃～220 ℃ as presoma, and wherein the mol ratio of molysite and mineralizer is 1:5～1:15.Average size of products 750 nanometers of hollow ball structure, wall thickness 250 nanometers.Electro-chemical test shows that this composite material is through after repeatedly circulating, and capacity still can remain on 720mAhg
-1, demonstrate excellent chemical property.
Chinese patent application CN201210261156.6 discloses a kind of carbon coated ferriferrous oxide lithium ion battery cathode material and its preparation method.This negative material is that carbon coats Fe
3O
4Composite material is nano particle, and its particle diameter is between 1～100nm; Its preparation process: adopt NaCl as dispersant and carrier, it is fully mixed with metal oxide source and solid carbon source; With mixed solution vacuumize, obtain mixture; Mixture is put into tube furnace under inert atmosphere, calcine, obtain calcined product; With the calcined product washing, grind and obtain the carbon-clad metal oxide nano particles.This method safety non-toxic, simple to operate, with the lithium-ion button battery of this material preparation in charge-discharge test, 0.1C(current density is 92mA/g) circulation 30 weeks after, specific discharge capacity can remain on 620～900mAh/g, in the 1C(current density is 920mA/g) after 50 weeks of circulation, specific discharge capacity still can remain on 600～760mAh/g, and this lithium ion battery negative material has higher reversible capacity and good cyclical stability.
Chinese patent application CN201210034375.0 discloses a kind of preparation method of tri-iron tetroxide/carbon nano tube compound material, be to be raw material with multi-walled carbon nano-tubes, iron ammonium sulfate, iron chloride and NaOH, polyvinyl alcohol is as surfactant, adopt reverse coprecipitation to obtain tri-iron tetroxide/carbon nano-tube magnetic nanometer composite material, by changing the concentration of reaction temperature and reaction solution, obtained the nanometer Fe of different-grain diameter size
3O
4Coating layer.The coating layer nanometer Fe of the tri-iron tetroxide/carbon nano tube compound material of this method preparation
3O
4Particle diameter is even, and the nano particle average grain diameter is less than 10nm, and synthesis technique and production equipment are simple, and the tri-iron tetroxide/carbon nano tube compound material that makes has magnetic.
Therefore, exploitation transition metal oxide/carbon composite has broad application prospects.
Summary of the invention
The invention provides the good and structure of a kind of electrochemical stability and be different from existing Fe
3O
4Tri-iron tetroxide/the carbon composite of the tubulose nucleocapsid structure of/C composite material.
The present invention also provides a kind of preparation method of tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure, and this method technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
It is compound that the present invention's discovery has the tri-iron tetroxide and the carbon of nano tube structure, because tri-iron tetroxide is in tubular construction and because the conduction and the buffering effect of carbon-coating, can effectively improve the chemical property of tri-iron tetroxide, the particularly cyclical stability in charge and discharge process.
A kind of tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure, form by ferriferrous oxide nano pipe and the carbon-coating (C) that is coated on the ferriferrous oxide nano pipe, having with ferriferrous oxide nano Guan Weihe and with the carbon-coating is the tubulose nucleocapsid structure of shell, and the molecular formula of described composite material is Fe
3O
4/ C.
In order further to improve the application performance of composite material, the weight percentage of carbon is preferably 1%～10% in the described composite material, and more preferably 4.1%～8.4%.
The present invention makes nano tube structure with tri-iron tetroxide, because the tubular structure of nanotube uniqueness, helps the embedding of lithium ion and deviates from, and the space in the pipe helps the buffering of volume.Therefore the present invention selects ferriferrous oxide nano Guan Weihe for use, and preferred, the length of described ferriferrous oxide nano pipe is 300 nanometers～800 nanometers, and external diameter is 70 nanometers～120 nanometers, and wall thickness is 5 nanometers～20 nanometers.
For conductivity and the cyclical stability that improves the ferriferrous oxide nano pipe, the ferriferrous oxide nano pipe is carried out carbon coat, preferred, the thickness of described carbon-coating is 2 nanometers～10 nanometers.
The preparation method of the tri-iron tetroxide/carbon composite of described tubulose nucleocapsid structure may further comprise the steps:
1) crystalline hydrate that will contain the salt of trivalent Fe or contain the salt of trivalent Fe is dissolved in the deionized water, obtains Fe
3+Concentration is the solution of 0.01mol/L～0.1mol/L;
2) in step 1) solution, add dihydric phosphate, be warming up to 150 ℃～250 ℃ after the sealing, react cooling after 12 hours～60 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying, obtain dried product, i.e. di-iron trioxide nanotube (Fe
2O
3);
3) with step 2) in dried product in the mixed atmosphere of forming by acetylene and nitrogen, carried out chemical vapor deposition (CVD) reaction 10 minutes～60 minutes in 200 ℃～600 ℃, cooling obtains end product tri-iron tetroxide/carbon composite.
In the step 1), the described salt that contains trivalent Fe can be selected the water miscible salt that contains trivalent Fe in this area for use, is preferably the fluoride of trivalent Fe, the chloride of trivalent Fe, the nitrate of trivalent Fe, the sulfate of trivalent Fe, the oxalates of trivalent Fe or the acetate of trivalent Fe.
Step 2) in, described dihydric phosphate plays corrosiveness, is used for the di-iron trioxide nanometer rods is corroded into the di-iron trioxide nanotube; Preferably, the mole addition of described dihydric phosphate is Fe
3+1/10～1/100 of mole.Described dihydric phosphate is preferably sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate.
Step 2) in, further preferred: as to be warming up to 200 ℃～240 ℃ after the sealing, to react cooling after 24 hours～48 hours; General reaction temperature is high more, and the time is long more, and the tube wall of di-iron trioxide nanotube is thin more, but little to the length and the external diameter influence of nanotube.
In the step 3), the volume ratio of acetylene and nitrogen is preferably 1:9 in the described mixed atmosphere, flow 100 cc/min.Under this condition, the deposition effect of carbon-coating is better, can access thickness carbon-coating uniformly.
In the step 3), further preferred: with step 2) in dried product in the mixed atmosphere of forming by acetylene and nitrogen, carried out chemical vapour deposition reaction 30 minutes～60 minutes in 350 ℃～450 ℃, cool off and obtain end product tri-iron tetroxide/carbon composite.Reaction temperature is high more as this step 1, and the time is long more, and carbon-coating is thick more, and the product phosphorus content is high more.
The qualification that described chilling temperature is not strict is operating as the master with suitable, generally can be cooled to 15 ℃～30 ℃ ambient temperature.
The tri-iron tetroxide of described tubulose nucleocapsid structure/carbon composite electrochemical stability is good, can be used as lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
1, the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure of the present invention is the tubulose nucleocapsid structure of shell owing to being with ferriferrous oxide nano Guan Weihe and with the carbon-coating, help the raising of diffusion, buffer volumes variation and the conductivity of lithium ion, therefore help the raising of the special cyclical stability of chemical property of composite material.
2, the tri-iron tetroxide of tubulose nucleocapsid structure of the present invention/carbon composite electrochemical stability is good, can be used as lithium ion battery negative material.
3, the present invention adopts the tri-iron tetroxide/carbon composite of hydro-thermal/CVD prepared in reaction tubulose nucleocapsid structure, has that technology is simple, cost is low, the cycle is short, energy consumption is low and is fit to advantage such as suitability for industrialized production.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained tri-iron tetroxide/carbon composite.
Fig. 2 is the stereoscan photograph of embodiment 1 gained tri-iron tetroxide/carbon composite;
Fig. 3 is the transmission electron microscope photo of embodiment 1 gained tri-iron tetroxide/carbon composite;
Fig. 4 is the high-resolution-ration transmission electric-lens photo of embodiment 1 gained tri-iron tetroxide/carbon composite;
Fig. 5 is embodiment 1 gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube chemical property figure.
Embodiment
With FeCl
36H
2O is dissolved in deionized water, is mixed with 80 milliliters of Fe
3+Concentration is the solution of 0.01mol/L, adds 9.6 milligrams of (0.0676mmol) sodium dihydrogen phosphates again, and it is 100 milliliters autoclave (compactedness 80% that mixed solution is placed capacity, percent by volume) in, with the reactor sealing, reacted 48 hours down then, naturally cool to room temperature at 220 ℃; Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, dry, (volume ratio of acetylene and nitrogen is 1:9 at acetylene/nitrogen with desciccate again, flow 100 cc/min) reacted 30 minutes in 450 ℃ of following CVD in the mixed atmosphere, obtain 0.064g tri-iron tetroxide/carbon composite, wherein, the weight percentage of carbon is 5.3%.
The X ray diffracting spectrum of gained composite material, stereoscan photograph, transmission electron microscope photo and high-resolution-ration transmission electric-lens photo are respectively as Fig. 1 to Fig. 4, and wherein the diffraction maximum of X ray all can be summed up as Fe
3O
4, can not find out the diffraction maximum of carbon from X ray diffracting spectrum, this is because the carbon crystallinity is relatively poor and content is lower.From stereoscan photograph, transmission electron microscope photo and high-resolution-ration transmission electric-lens photo as can be seen, it is the tubulose nucleocapsid structure of shell that the gained composite material presents with ferriferrous oxide nano Guan Weihe and with the carbon-coating, wherein the length of ferriferrous oxide nano tube nucleus is 300 nanometers～800 nanometers, external diameter is 70 nanometers～120 nanometers, wall thickness is 10 nanometers～15 nanometers, and the carbon-coating thickness of the shell is 4 nanometers～5 nanometers.
Carry out electrochemical property test (constant current charge-discharge in the certain voltage scope) with gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube (being desciccate) as lithium ion battery negative material respectively, gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube chemical property such as Fig. 5, constant current charge-discharge (current density 100mAg
-1, voltage range 0.01～3V) test shows, cycle-index are 1 o'clock, the capacity of tri-iron tetroxide/carbon composite is 698mAhg
-1, cycle-index is 30 o'clock, the capacity of tri-iron tetroxide/carbon composite only is reduced to 681mAhg
-1And cycle-index is 1 o'clock, and the capacity of di-iron trioxide nanotube is 621mAhg
-1, cycle-index is 30 o'clock, it only is 89mAhg that the capacity of di-iron trioxide nanotube reduces rapidly
-1As seen compare with the di-iron trioxide nanotube, the cyclical stability of tri-iron tetroxide/carbon composite of the present invention obviously improves, and electrochemical stability is good; And the cyclical stability of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure of the present invention is good, can be used as a kind of new lithium ion battery negative material.
Embodiment 2
With Fe (NO
3)
39H
2O is dissolved in deionized water, is mixed with 80 milliliters of Fe
3+Concentration is the solution of 0.03mol/L, adds 10.9 milligrams of (0.08mmol) potassium dihydrogen phosphates again, and it is 100 milliliters autoclave (compactedness 80% that mixed solution is placed capacity, percent by volume) in, with the reactor sealing, reacted 36 hours down then, naturally cool to room temperature at 240 ℃; Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, dry, (volume ratio of acetylene and nitrogen is 1:9 at acetylene/nitrogen with desciccate again, flow 100 cc/min) reacted 45 minutes in 400 ℃ of following CVD in the mixed atmosphere, obtain 0.183g tri-iron tetroxide/carbon composite, wherein, the weight percentage of carbon is 7.5%.
From the X ray diffracting spectrum of gained composite material as can be known, the diffraction maximum of product all can be summed up as Fe
3O
4, can not find out the diffraction maximum of carbon from X ray diffracting spectrum, this is because the carbon crystallinity is relatively poor and content is lower.From stereoscan photograph, transmission electron microscope photo and the high-resolution-ration transmission electric-lens photo of gained composite material as can be seen, it is the tubulose nucleocapsid structure of shell that the gained composite material presents with ferriferrous oxide nano Guan Weihe and with the carbon-coating, wherein the length of ferriferrous oxide nano tube nucleus is 300 nanometers～800 nanometers, external diameter is 70 nanometers～120 nanometers, wall thickness is 17 nanometers～18 nanometers, and the carbon-coating thickness of the shell is 7 nanometers～8 nanometers.
Carry out electrochemical property test (constant current charge-discharge in the certain voltage scope) with gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube (being desciccate) as lithium ion battery negative material respectively, gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube chemical property, constant current charge-discharge (current density 100mAg
-1, voltage range 0.01～3V) test shows, cycle-index are 1 o'clock, the capacity of tri-iron tetroxide/carbon composite is 701mAhg
-1, cycle-index is 30 o'clock, the capacity of tri-iron tetroxide/carbon composite only is reduced to 675mAhg
-1And cycle-index is 1 o'clock, and the capacity of di-iron trioxide nanotube is 671mAhg
-1, cycle-index is 30 o'clock, it only is 106mAhg that the capacity of di-iron trioxide nanotube reduces rapidly
-1As seen compare with the di-iron trioxide nanotube, the cyclical stability of tri-iron tetroxide/carbon composite obviously improves, and electrochemical stability is good; And the cyclical stability of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure of the present invention is good, can be used as a kind of new lithium ion battery negative material.
Embodiment 3
With Fe
2(SO
4)
3Be dissolved in deionized water, be mixed with 80 milliliters of Fe
3+Concentration is the solution of 0.05mol/L, adds 9.6 milligrams of (0.0676mmol) sodium dihydrogen phosphates again, and it is 100 milliliters autoclave (compactedness 80% that mixed solution is placed capacity, percent by volume) in, with the reactor sealing, reacted 24 hours down then, naturally cool to room temperature at 200 ℃; Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, dry, (volume ratio of acetylene and nitrogen is 1:9 at acetylene/nitrogen with desciccate again, flow 100 cc/min) reacted 30 minutes in 400 ℃ of following CVD in the mixed atmosphere, obtain 0.310g tri-iron tetroxide/carbon composite, wherein, the weight percentage of carbon is 4.1%.
From the X ray diffracting spectrum of gained composite material as can be known, the diffraction maximum of product all can be summed up as Fe
3O
4, can not find out the diffraction maximum of carbon from X ray diffracting spectrum, this is because the carbon crystallinity is relatively poor and content is lower.From stereoscan photograph, transmission electron microscope photo and the high-resolution-ration transmission electric-lens photo of gained composite material as can be seen, it is the tubulose nucleocapsid structure of shell that the gained composite material presents with ferriferrous oxide nano Guan Weihe and with the carbon-coating, wherein the length of ferriferrous oxide nano tube nucleus is 300 nanometers～800 nanometers, external diameter is 70 nanometers～120 nanometers, wall thickness is 18 nanometers～20 nanometers, and the carbon-coating thickness of the shell is 3 nanometers～4 nanometers.
(be desciccate with gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube respectively,) carry out electrochemical property test (constant current charge-discharge in the certain voltage scope) as lithium ion battery negative material, gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube chemical property, constant current charge-discharge (current density 100mAg
-1, voltage range 0.01～3V) test shows, cycle-index are 1 o'clock, the capacity of tri-iron tetroxide/carbon composite is 688mAhg
-1, cycle-index is 30 o'clock, the capacity of tri-iron tetroxide/carbon composite only is reduced to 656mAhg
-1And cycle-index is 1 o'clock, and the capacity of di-iron trioxide nanotube is 668mAhg
-1, cycle-index is 30 o'clock, it only is 96mAhg that the capacity of di-iron trioxide nanotube reduces rapidly
-1As seen compare with the di-iron trioxide nanotube, the cyclical stability of tri-iron tetroxide/carbon composite obviously improves, and electrochemical stability is good; And the cyclical stability of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure of the present invention is good, can be used as a kind of new lithium ion battery negative material.
With FeCl
36H
2O is dissolved in deionized water, is mixed with 80 milliliters of Fe
3+Concentration is the solution of 0.1mol/L, adds 9.2 milligrams of (0.08mmol) ammonium dihydrogen phosphates again, and it is 100 milliliters autoclave (compactedness 80% that mixed solution is placed capacity, percent by volume) in, with the reactor sealing, reacted 48 hours down then, naturally cool to room temperature at 240 ℃; Collect solid reaction product, product is washed through deionized water and absolute ethyl alcohol alternate repetition, dry, (volume ratio of acetylene and nitrogen is 1:9 at acetylene/nitrogen with desciccate again, flow 100 cc/min) reacted 60 minutes in 350 ℃ of following CVD in the mixed atmosphere, obtain 0.655g tri-iron tetroxide/carbon composite, wherein, the weight percentage of carbon is 8.4%.
From the X ray diffracting spectrum of gained composite material as can be known, the diffraction maximum of product all can be summed up as Fe
3O
4, can not find out the diffraction maximum of carbon from X ray diffracting spectrum, this is because the carbon crystallinity is relatively poor and content is lower.From stereoscan photograph, transmission electron microscope photo and the high-resolution-ration transmission electric-lens photo of gained composite material as can be seen, it is the tubulose nucleocapsid structure of shell that the gained composite material presents with ferriferrous oxide nano Guan Weihe and with the carbon-coating, wherein the length of ferriferrous oxide nano tube nucleus is 300 nanometers～800 nanometers, external diameter is 70 nanometers～120 nanometers, wall thickness is 8 nanometers～12 nanometers, and the carbon-coating thickness of the shell is 8 nanometers～9 nanometers.
Carry out electrochemical property test (constant current charge-discharge in the certain voltage scope) with gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube (being desciccate) as lithium ion battery negative material respectively, gained tri-iron tetroxide/carbon composite and di-iron trioxide nanotube chemical property, constant current charge-discharge (current density 100mAg
-1, voltage range 0.01～3V) test shows, cycle-index are 1 o'clock, the capacity of tri-iron tetroxide/carbon composite is 712mAhg
-1, cycle-index is 30 o'clock, the capacity of tri-iron tetroxide/carbon composite only is reduced to 688mAhg
-1And cycle-index is 1 o'clock, and the capacity of di-iron trioxide nanotube is 679mAhg
-1, cycle-index is 30 o'clock, it only is 121mAhg that the capacity of di-iron trioxide nanotube reduces rapidly
-1As seen compare with the di-iron trioxide nanotube, the cyclical stability of tri-iron tetroxide/carbon composite obviously improves, and electrochemical stability is good; And the cyclical stability of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure of the present invention is good, can be used as a kind of new lithium ion battery negative material.
In addition, in scope of the present invention, for example substitute the salt of the Fe in the foregoing description with the crystalline hydrate that other contains the salt of trivalent Fe or contains the salt of trivalent Fe of the present invention, with the reaction condition in the alternative the foregoing description of reaction condition of the present invention, the composite material that makes all has the tubulose nucleocapsid structure, and cyclical stability is good.
Claims (10)
1. tri-iron tetroxide/the carbon composite of a tubulose nucleocapsid structure, it is characterized in that, be made up of ferriferrous oxide nano pipe and the carbon-coating that is coated on the ferriferrous oxide nano pipe, having with ferriferrous oxide nano Guan Weihe and with the carbon-coating is the tubulose nucleocapsid structure of shell.
2. tri-iron tetroxide/the carbon composite of tubulose nucleocapsid structure according to claim 1 is characterized in that, the weight percentage of carbon-coating is 1%～10% in the described composite material.
3. tri-iron tetroxide/the carbon composite of tubulose nucleocapsid structure according to claim 1 and 2 is characterized in that, the thickness of described carbon-coating is 2 nanometers～10 nanometers.
4. tri-iron tetroxide/the carbon composite of tubulose nucleocapsid structure according to claim 1 is characterized in that, the length of described ferriferrous oxide nano pipe is 300 nanometers～800 nanometers, and external diameter is 70 nanometers～120 nanometers, and wall thickness is 5 nanometers～20 nanometers.
5. according to the preparation method of the tri-iron tetroxide/carbon composite of each described tubulose nucleocapsid structure of claim 1～4, it is characterized in that, may further comprise the steps:
1) crystalline hydrate that will contain the salt of trivalent Fe or contain the salt of trivalent Fe is dissolved in the deionized water, obtains Fe
3+Concentration is the solution of 0.01mol/L～0.1mol/L;
2) add dihydric phosphate in step 1) solution, be warming up to 150 ℃～250 ℃ after the sealing, react cooling after 12 hours～60 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains dried product;
3) with step 2) in dried product in the mixed atmosphere of forming by acetylene and nitrogen, carried out chemical vapour deposition reaction 10 minutes～60 minutes in 200 ℃～600 ℃, cooling obtains end product tri-iron tetroxide/carbon composite.
6. the preparation method of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure according to claim 5, it is characterized in that, in the step 1), the nitrate of the fluoride that the described salt that contains trivalent Fe is trivalent Fe, the chloride of trivalent Fe, trivalent Fe, the sulfate of trivalent Fe, the oxalates of trivalent Fe or the acetate of trivalent Fe.
7. the preparation method of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure according to claim 5 is characterized in that step 2) in, the mole addition of described dihydric phosphate is Fe
3+1/10～1/100 of mole.
8. according to the preparation method of the tri-iron tetroxide/carbon composite of claim 5 or 7 described tubulose nucleocapsid structures, it is characterized in that step 2) in, described dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate.
9. the preparation method of the tri-iron tetroxide/carbon composite of tubulose nucleocapsid structure according to claim 5 is characterized in that, in the step 3), the volume ratio of acetylene and nitrogen is 1:9 in the described mixed atmosphere, flow 100 cc/min.
10. according to the application of the tri-iron tetroxide/carbon composite of each described tubulose nucleocapsid structure of claim 1～4, it is characterized in that the tri-iron tetroxide/carbon composite of described tubulose nucleocapsid structure is as the application in the lithium ion battery negative material.
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| CN103825019A (en) * | 2014-02-21 | 2014-05-28 | 浙江大学 | Fe3O4/C composite material, its preparation method and its application in lithium ion battery |
| CN106848256A (en) * | 2017-03-24 | 2017-06-13 | 中南大学 | A kind of nickel iron cell core duplex shell structure negative pole nano material and its preparation method and application |
| CN108574129A (en) * | 2017-03-09 | 2018-09-25 | 天津大学 | A kind of high temperature resistant calcining iron oxide nanotube electrode and its preparation method and application |
| CN110323442A (en) * | 2019-07-17 | 2019-10-11 | 中国科学院福建物质结构研究所 | A kind of carbon coating Fe3O4Composite material and preparation method and application |
| CN112537797A (en) * | 2020-12-07 | 2021-03-23 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN113540462A (en) * | 2021-07-02 | 2021-10-22 | 浙江大学 | Ferric oxide-based negative electrode binder of lithium ion battery |
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Cited By (8)
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| CN103825019A (en) * | 2014-02-21 | 2014-05-28 | 浙江大学 | Fe3O4/C composite material, its preparation method and its application in lithium ion battery |
| CN108574129A (en) * | 2017-03-09 | 2018-09-25 | 天津大学 | A kind of high temperature resistant calcining iron oxide nanotube electrode and its preparation method and application |
| CN106848256A (en) * | 2017-03-24 | 2017-06-13 | 中南大学 | A kind of nickel iron cell core duplex shell structure negative pole nano material and its preparation method and application |
| CN106848256B (en) * | 2017-03-24 | 2019-06-21 | 中南大学 | A kind of nickel iron cell core duplex shell structure cathode nano material and its preparation method and application |
| CN110323442A (en) * | 2019-07-17 | 2019-10-11 | 中国科学院福建物质结构研究所 | A kind of carbon coating Fe3O4Composite material and preparation method and application |
| CN112537797A (en) * | 2020-12-07 | 2021-03-23 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN112537797B (en) * | 2020-12-07 | 2023-04-18 | 安徽师范大学 | Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application |
| CN113540462A (en) * | 2021-07-02 | 2021-10-22 | 浙江大学 | Ferric oxide-based negative electrode binder of lithium ion battery |
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