CN110518230A - The preparation method of lithium ion battery negative material - Google Patents
The preparation method of lithium ion battery negative material Download PDFInfo
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- CN110518230A CN110518230A CN201910903083.8A CN201910903083A CN110518230A CN 110518230 A CN110518230 A CN 110518230A CN 201910903083 A CN201910903083 A CN 201910903083A CN 110518230 A CN110518230 A CN 110518230A
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to a kind of preparation methods of lithium ion battery negative material, belong to nanocomposite preparation field.Di-iron trioxide (the Fe of pure phase is prepared by hydro-thermal reaction first2O3), then successively in di-iron trioxide outer cladding layer of silicon dioxide and carbon-coating, then so that material is formed a kind of yolk shell structure by etching away silica, finally form the di-iron trioxide/carbon/trimanganese tetroxide nano composite material with yolk shell structure in one layer of mangano-manganic oxide of carbon-coating outer cladding.For carbon shell while promoting electron-transport, the cavity between di-iron trioxide core provides additional free space to mitigate structural strain, reduces shell caused by large volume changes and destroys, to keep structural intergrity.In the manganic manganous oxide nano-material of carbon-coating to buffer ess-strain and enhance the kinetic characteristics of hybrid material with the synergistic effect of di-iron trioxide and carbon-coating, excellent performance is shown.When the material is applied to lithium cell cathode material, good charge/discharge capacity and cyclical stability are shown.
Description
Technical field
The present invention relates to nanocomposite preparation field, in particular to a kind of preparation side of yolk core-shell structure composite material
Method, espespecially a kind of preparation method of lithium ion battery negative material.By successively coated with carbon bed and mangano-manganic oxide come
Improve charge/discharge capacity and cyclical stability of the di-iron trioxide as lithium cell cathode material.
Background technique
Environmental problem get worse and to find sustainable energy serious hope excite people constantly develop high-performance,
Cleaning and renewable energy storage device.Rechargeable lithium ion batteries with its high-energy density, long circulation life, low self-discharge,
The advantages that memory-less effect and environment friendly, in the energy storage devices such as various portable electronic devices and new-energy automobile
Extensive use is arrived.Current commercialized anode material is graphitic carbon, has good cyclical stability, but theoretical capacity is opposite
Lower (theoretical specific capacity is 372 every gram of milliampere hour).Therefore, suitable high performance anode material is found to substitute current business
The graphitization lithium ion battery material of change is meaningful.Metal oxide has specific capacity is high, is easy to large scale preparation etc.
Advantage has always been considered as being potential anode of lithium ion battery candidate material for a long time.However it is being applied to lithium ion battery
When negative electrode material, transition metal oxide comes with some shortcomings, such as finite conductivity in lithium ion insertion/extraction process, ion
Transport that dynamics is poor and electrochemical reaction process in a large amount of volume expansion and shrink the dusting for leading to metal oxide and poly-
Collection becomes problem to be solved so as to shorten cycle life etc..
As a member of metal oxide, di-iron trioxide is since (1007 milliampere hour are every for its theoretical capacity with higher
Gram), natural richness and environment friendly and cause the broad interest of people.Such as in the prior art " " Core-shell
Mn3O4 nanorods with porous Fe2O3 layer supported on graphemeconductive
Nanosheets for high-performance lithium storage application ", Wang et al.,
It is mentioned in Composites Part B:Engineering, Volume 167,15 June 2019, Pages 668-675 "
After mangano-manganic oxide and di-iron trioxide are compound, cross-linked structure and synergistic effect both contribute to improve the storage of lithium ion battery
Its charge/discharge capacity and cyclical stability can be improved in lithium performance and dynamic characteristic.Such as in the prior art " " Robust
erythrocyte-like Fe2O3@carbon with yolk-shell structures as
Highperformanceanode for lithium ion batteries " Zheng et al., Chemical
Three oxidations are mentioned in Engineering Journal, Volume 347,1 September 2018, Pages 563-573 "
Two iron and carbon are formed after composite material, improve whole electric conductivity, while in constant current charge-discharge capacity and high rate performance
On be all obviously improved.Although di-iron trioxide prepared by two kinds of technologies and its compound are equal relative to commercial graphite
With higher charge/discharge capacity, but it is still up for further being promoted.What must still be solved at present is exactly to promote three oxidations
The lower problem of the cyclical stability and specific discharge capacity of two iron.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of lithium ion battery negative material, solve the prior art and deposit
The above problem.The invention proposes in this unique texture, carbon shell is while promoting electron-transport, with di-iron trioxide
Between cavity provide additional free space to mitigate structural strain, during avoiding lithium ion insertion/extraction cycle
Volume change caused by strain, reduce large volume change caused by shell destroy, to keep structural intergrity.In carbon
The manganic manganous oxide nano-material of layer is to buffer ess-strain and enhance hydridization with the synergistic effect of di-iron trioxide and carbon-coating
The kinetic characteristics of material, so that the charge/discharge capacity of composite material is further promoted.And synthetic method is environmental-friendly, system
Standby di-iron trioxide/carbon/mangano-manganic oxide yolk shell structure lithium cell cathode material electrochemical performance, in 200 millis
Pacify under every gram of current density, its specific discharge capacity is still able to maintain 1056 every gram of milliampere hour after 100 circle circulations, and shows excellent
Cyclical stability.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
The preparation method of lithium ion battery negative material, includes the following steps:
Step (1), hydro-thermal method prepare pure phase ferric oxide powder: 1-10 grams of ferric chloride hexahydrate is dissolved in 50-100 milliliters of water
In, then respectively by 5-15 grams of sodium acetate trihydrate, 1-5 grams of cetyl trimethylammonium bromide, 15-30 milliliters of ethylenediamine solutions add
Enter in above-mentioned solution, stirs 5-15 minutes, be placed in reaction kettle, reacted 8-15 hours under 150-220 degrees Celsius, be cooled to room
Temperature obtains the ferric oxide powder of pure phase after centrifuge washing；
Step (2) prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
Last 0.5-1 grams is dissolved in 300-600 milliliters of ethyl alcohol, and 1.5-2.5 milliliters of tetraethoxysilanes are added, and stirring is added after 2-5 hours
5-15 milliliters of ammonium hydroxide and 30-60 ml deionized water stir 3-6 hours, after centrifugation, washing, drying, then the 200- in tube furnace
Di-iron trioxide/silicon dioxide nano composite material is handled 1-6 hours to obtain under 450 degrees Celsius；
Step (3) prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/titanium dioxide obtained in step (2)
0.2-0.7 grams of silicon nanocomposite is dissolved in 10-20 milliliters of water, and 0.1-0.5 grams of cetyl trimethylammonium bromide is added, stirs
After mixing 10-20 minutes, 0.1-0.5 grams of resorcinol, 10-30 milliliters of dehydrated alcohols, 0.05-0.15 milliliters of ammonium hydroxide, In are added
0.01-0.1 milliliters of formaldehyde are added after stirring 15-45 minutes in 20-45 C water bath, after stirring in 4-10 hours, centrifugation is washed
It washs, after being then sintered 1-6 hours under 450-700 degrees Celsius, is etched one day with sodium hydroxide solution, centrifuge washing is up to yolk
Shell structure di-iron trioxide/carbon nano-composite material；
Step (4) prepares di-iron trioxide/carbon/trimanganese tetroxide nano composite material: taking 40-100 milligrams of step (3) preparations
Sample be dissolved in 15-40 milliliters of water, the manganese nitrate solution of 0.05-0.15 grams of potassium permanganate and 40-80 milliliter 50% is added respectively
Enter above-mentioned solution, is handled 30-90 minutes in 50-100 C water bath；After centrifugal drying, then under 500-750 degrees Celsius
Sintering 30-90 minutes, finally obtains di-iron trioxide/carbon/trimanganese tetroxide nano composite material.
The beneficial effects of the present invention are:
(1) di-iron trioxide/carbon/mangano-manganic oxide composite material of the invention is by center di-iron trioxide, intermediate carbon-coating and outer
Layer mangano-manganic oxide three parts composition, carbonaceous material completely envelope intermediate di-iron trioxide, three are effectively contacted
Together, the electric conductivity of composite material is effectively improved, and then improves the overall performance of composite material.
(2) in di-iron trioxide/carbon/mangano-manganic oxide composite material of the invention, carbonaceous material is completely enveloping three
While aoxidizing two iron, the cavity between di-iron trioxide provides additional free space to mitigate structural strain, reduces
Shell caused by large volume changes destroys, to maintain structural intergrity and cyclical stability.
(3) in di-iron trioxide/carbon/mangano-manganic oxide composite material of the invention, in the trimanganese tetroxide nano of carbon-coating
While material is to buffer ess-strain, the dynamics for enhancing hybrid material with the synergistic effect of di-iron trioxide and carbon-coating is special
Property, so that the charge/discharge capacity of composite material has obtained greatly being promoted.
(4) in di-iron trioxide/carbon of the invention/mangano-manganic oxide composite material preparation process, synthetic method environment
It is friendly pollution-free, also significantly reduce preparation cost.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, this hair
Bright illustrative example and its explanation is used to explain the present invention, and is not constituted improper limitations of the present invention.
Fig. 1 is the scanning electron microscope (SEM) photograph of di-iron trioxide prepared by the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of di-iron trioxide/carbon composite prepared by the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention；
Fig. 4 is the transmission electron microscope picture of di-iron trioxide prepared by the present invention；
Fig. 5 is the transmission electron microscope picture of di-iron trioxide/carbon composite prepared by the present invention；
Fig. 6 is the transmission electron microscope picture of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention；
Fig. 7 is di-iron trioxide prepared by the present invention, di-iron trioxide/carbon composite and di-iron trioxide/carbon/tetra- oxidations
The X-ray diffractogram of three manganese composite materials；
Fig. 8 is the cyclic curve figure of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention；
Fig. 9 is the curve of double curvature figure of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention.
Specific embodiment
Detailed content and its specific embodiment of the invention are further illustrated with reference to the accompanying drawing.
Referring to shown in Fig. 1 to Fig. 9, the preparation method of lithium ion battery negative material of the invention is anti-by hydro-thermal first
Di-iron trioxide (the Fe of pure phase should be prepared2O3), then successively in di-iron trioxide outer cladding layer of silicon dioxide and carbon-coating,
Then material is made to form a kind of yolk shell structure by etching away silica, finally in one layer of mangano-manganic oxide of carbon-coating outer cladding
Form the di-iron trioxide/carbon/trimanganese tetroxide nano composite material with yolk shell structure.Carbon shell is promoting electron-transport
Meanwhile the cavity between di-iron trioxide core provides additional free space to mitigate structural strain, reduces large volume
Shell caused by changing destroys, to keep structural intergrity.It is answered in the manganic manganous oxide nano-material of carbon-coating with buffering stress
Become and enhance the kinetic characteristics of hybrid material with the synergistic effect of di-iron trioxide and carbon-coating, shows excellent performance.
When the material is applied to lithium cell cathode material, good charge/discharge capacity and cyclical stability are shown.Specific steps are such as
Under:
Step (1), hydro-thermal method prepare pure phase ferric oxide powder: 1-10 grams of ferric chloride hexahydrate is dissolved in 50-100 milliliters of water
In, then respectively by 5-15 grams of sodium acetate trihydrate, 1-5 grams of cetyl trimethylammonium bromide, 15-30 milliliters of ethylenediamine solutions add
Enter in above-mentioned solution, stirs 5-15 minutes, be placed in reaction kettle, reacted 8-15 hours under 150-220 degrees Celsius, be cooled to room
Temperature obtains the ferric oxide powder of pure phase after centrifuge washing.
Step (2) prepares di-iron trioxide/silicon dioxide nano composite material: taking three oxidation two obtained in step (1)
0.5-1 grams of iron powder is dissolved in 300-600 milliliters of ethyl alcohol, 1.5-2.5 milliliters of tetraethoxysilanes is added, after stirring 2-5 hours
5-15 milliliters of ammonium hydroxide and 30-60 ml deionized water is added, stirs 3-6 hours, after centrifugation, washing, drying, then in tube furnace
Di-iron trioxide/silicon dioxide nano composite material is handled 1-6 hours to obtain under 200-450 degrees Celsius.
Step (3) prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/bis- obtained in step (2)
0.2-0.7 grams of silica nanocomposite is dissolved in 10-20 milliliters of water, and 0.1-0.5 grams of cetyl trimethyl bromination is added
Ammonium adds 0.1-0.5 grams of resorcinol, 10-30 milliliters of dehydrated alcohols, 0.05-0.15 milliliters of ammonia after stirring 10-20 minutes
0.01-0.1 milliliters of formaldehyde are added in water after stirring 15-45 minutes in 20-45 C water bath, after stirring in 4-10 hours, from
Heart washing after being then sintered 1-6 hours under 450-700 degrees Celsius, is etched one day, centrifuge washing with sodium hydroxide solution to obtain the final product
Yolk shell structure di-iron trioxide/carbon nano-composite material.
Step (4) prepares di-iron trioxide/carbon/trimanganese tetroxide nano composite material: taking 40-100 milligrams of steps (3)
The sample of preparation is dissolved in 15-40 milliliters of water, by the manganese nitrate solution of 0.05-0.15 grams of potassium permanganate and 40-80 milliliter 50% point
Above-mentioned solution is not added, is handled 30-90 minutes in 50-100 C water bath.It is Celsius after centrifugal drying, then in 500-750
Degree lower sintering 30-90 minutes, finally obtain di-iron trioxide/carbon/trimanganese tetroxide nano composite material.
Embodiment 1:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 6 grams of ferric chloride hexahydrates being dissolved in 90 milliliters of water, then respectively will
9.9569 grams of sodium acetate trihydrates, 2.9963 grams of cetyl trimethylammonium bromides, 21 milliliters of ethylenediamine solutions are added above-mentioned molten
It in liquid, stirs 10 minutes, is placed in reaction kettle, react 10 hours, be cooled to room temperature at 200 degrees celsius, after centrifuge washing,
Obtain the ferric oxide powder of pure phase.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.93184 gram of end is dissolved in 560 milliliters of ethyl alcohol, and 2 milliliters of tetraethoxysilanes are added, 10 milliliters of ammonium hydroxide are added after stirring 3 hours
It with 40 ml deionized waters, stirs 4 hours, centrifugation is washed, after drying, then handled 4 hours under 350 degrees Celsius in tube furnace
Obtain di-iron trioxide/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.5 gram of nanocomposite is dissolved in 15 milliliters of water, and 0.23 gram of cetyl trimethylammonium bromide is added, after stirring 15 minutes,
0.35 gram of resorcinol, 28.2 milliliters of dehydrated alcohols are added, 0.1 milliliter of ammonium hydroxide stirs 30 minutes in 35 C water baths
0.05 milliliter of formaldehyde is added afterwards, after stirring in 6 hours, centrifuge washing uses hydrogen-oxygen after being then sintered 3 hours under 550 degrees Celsius
Change sodium solution to etch one day, centrifuge washing is up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 54 milligrams of steps (3) to prepare
It is dissolved in 35 milliliters of water, 0.108 gram of potassium permanganate and 67.5 milliliter 50% of manganese nitrate solution is separately added into above-mentioned solution, In
It is handled 60 minutes in 80 C water baths.It is sintered 60 minutes after centrifugal drying, then under 600 degrees Celsius, finally obtains three oxygen
Change two iron/carbon/trimanganese tetroxide nano composite material.
Embodiment 2:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 2 grams of ferric chloride hexahydrates being dissolved in 50 milliliters of water, then respectively by 5
Gram sodium acetate trihydrate, 1 gram of cetyl trimethylammonium bromide, 15 milliliters of ethylenediamine solutions are added in above-mentioned solution, stir 5 points
Clock is placed in reaction kettle, is reacted 8 hours, is cooled to room temperature under 150 degrees Celsius, after centrifuge washing, obtains three oxygen of pure phase
Change two iron powders.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.5 gram of end is dissolved in 300 milliliters of ethyl alcohol, and 1.5 milliliters of tetraethoxysilanes are added, 5 milliliters of ammonium hydroxide and 30 are added after stirring 2 hours
Ml deionized water stirs 3 hours, handles 1 hour after centrifugation, washing, drying, then in tube furnace under 200 degrees Celsius and obtains three
Aoxidize two iron/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.2 gram of nanocomposite is dissolved in 10 milliliters of water, and 0.1 gram of cetyl trimethylammonium bromide is added, and stirs after ten minutes, then
0.1 gram of resorcinol, 10 milliliters of dehydrated alcohols is added, 0.05 milliliter of ammonium hydroxide adds after stirring 15 minutes in 20 C water baths
Enter 0.01 milliliter of formaldehyde, after stirring in 4 hours, centrifuge washing uses sodium hydroxide after being then sintered 1 hour under 450 degrees Celsius
Solution etches one day, centrifuge washing was up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 40 milligrams of steps (3) to prepare
Product are dissolved in 15 milliliters of water, 0.05 gram of potassium permanganate and 40 milliliter 50% of manganese nitrate solution are separately added into above-mentioned solution, 50
It is handled 30 minutes in C water bath.It is sintered 30 minutes after centrifugal drying, then under 500 degrees Celsius, finally obtains three oxidations
Two iron/carbon/trimanganese tetroxide nano composite material.
Embodiment 3:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 3 grams of ferric chloride hexahydrates being dissolved in 60 milliliters of water, then respectively by 6
Gram sodium acetate trihydrate, 2 grams of cetyl trimethylammonium bromides, 18 milliliters of ethylenediamine solutions are added in above-mentioned solution, stir 6 points
Clock is placed in reaction kettle, is reacted 9 hours, is cooled to room temperature under 160 degrees Celsius, after centrifuge washing, obtains three oxygen of pure phase
Change two iron powders.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.6 gram of end is dissolved in 350 milliliters of ethyl alcohol, is added 1.6 milliliters of tetraethoxysilanes, be added after stirring 2.5 hours 6 milliliters of ammonium hydroxide and
35 ml deionized waters stir 3.5 hours, and centrifugation is washed, after drying, then handled 2 hours under 250 degrees Celsius in tube furnace
Obtain di-iron trioxide/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.3 gram of nanocomposite is dissolved in 11 milliliters of water, and 0.2 gram of cetyl trimethylammonium bromide is added, after stirring 11 minutes, then
0.2 gram of resorcinol, 15 milliliters of dehydrated alcohols is added, 0.06 milliliter of ammonium hydroxide stirs in 25 C water baths and adds after twenty minutes
Enter 0.02 milliliter of formaldehyde, after stirring in 5 hours, centrifuge washing uses sodium hydroxide after being then sintered 2 hours under 500 degrees Celsius
Solution etches one day, centrifuge washing was up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 50 milligrams of steps (3) to prepare
Product are dissolved in 20 milliliters of water, 0.06 gram of potassium permanganate and 45 milliliter 50% of manganese nitrate solution are separately added into above-mentioned solution, 60
It is handled 40 minutes in C water bath.It is sintered 40 minutes after centrifugal drying, then under 550 degrees Celsius, finally obtains three oxidations
Two iron/carbon/trimanganese tetroxide nano composite material.
Embodiment 4:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 4 grams of ferric chloride hexahydrates being dissolved in 70 milliliters of water, then respectively by 7
Gram sodium acetate trihydrate, 2.5 grams of cetyl trimethylammonium bromides, 20 milliliters of ethylenediamine solutions are added in above-mentioned solution, stirring 7
Minute, it is placed in reaction kettle, is reacted 11 hours under 170 degrees Celsius, be cooled to room temperature, after centrifuge washing, obtain pure phase
Ferric oxide powder.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.7 gram of end is dissolved in 400 milliliters of ethyl alcohol, is added 1.7 milliliters of tetraethoxysilanes, be added after stirring 3.5 hours 7 milliliters of ammonium hydroxide and
45 ml deionized waters stir 4.5 hours, and centrifugation is washed, after drying, then handled 3 hours under 300 degrees Celsius in tube furnace
Obtain di-iron trioxide/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.4 gram of nanocomposite is dissolved in 12 milliliters of water, and 0.3 gram of cetyl trimethylammonium bromide is added, after stirring 12 minutes, then
0.3 gram of resorcinol, 20 milliliters of dehydrated alcohols is added, 0.07 milliliter of ammonium hydroxide adds after stirring 25 minutes in 30 C water baths
Enter 0.03 milliliter of formaldehyde, after stirring in 7 hours, centrifuge washing uses sodium hydroxide after being then sintered 4 hours under 600 degrees Celsius
Solution etches one day, centrifuge washing was up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 60 milligrams of steps (3) to prepare
It is dissolved in 25 milliliters of water, 0.07 gram of potassium permanganate and 50 milliliter 50% of manganese nitrate solution is separately added into above-mentioned solution, taken the photograph 70
It is handled 50 minutes in family name's degree water-bath.It is sintered 50 minutes after centrifugal drying, then under 650 degrees Celsius, finally obtains three oxidations two
Iron/carbon/trimanganese tetroxide nano composite material.
Embodiment 5:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 5 grams of ferric chloride hexahydrates being dissolved in 80 milliliters of water, then respectively by 8
Gram sodium acetate trihydrate, 3.5 grams of cetyl trimethylammonium bromides, 25 milliliters of ethylenediamine solutions are added in above-mentioned solution, stirring 8
Minute, it is placed in reaction kettle, is reacted 12 hours under 180 degrees Celsius, be cooled to room temperature, after centrifuge washing, obtain pure phase
Ferric oxide powder.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.8 gram of end is dissolved in 450 milliliters of ethyl alcohol, and 1.8 milliliters of tetraethoxysilanes are added, 8 milliliters of ammonium hydroxide and 50 are added after stirring 4 hours
Ml deionized water stirs 5 hours, handles 5 hours after centrifugation, washing, drying, then in tube furnace under 400 degrees Celsius and obtains three
Aoxidize two iron/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.6 gram of nanocomposite is dissolved in 13 milliliters of water, and 0.4 gram of cetyl trimethylammonium bromide is added, after stirring 13 minutes, then
0.4 gram of resorcinol, 25 milliliters of dehydrated alcohols is added, 0.08 milliliter of ammonium hydroxide adds after stirring 35 minutes in 40 C water baths
Enter 0.04 milliliter of formaldehyde, after stirring in 8 hours, centrifuge washing uses sodium hydroxide after being then sintered 5 hours under 650 degrees Celsius
Solution etches one day, centrifuge washing was up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 70 milligrams of steps (3) to prepare
Product are dissolved in 30 milliliters of water, 0.08 gram of potassium permanganate and 55 milliliter 50% of manganese nitrate solution are separately added into above-mentioned solution, 90
It is handled 70 minutes in C water bath.It is sintered 70 minutes after centrifugal drying, then under 700 degrees Celsius, finally obtains three oxidations
Two iron/carbon/trimanganese tetroxide nano composite material.
Embodiment 6:
A kind of preparation method of lithium ion battery negative material, includes the following steps:
(1) hydro-thermal method prepares pure phase ferric oxide powder: 7 grams of ferric chloride hexahydrates being dissolved in 100 milliliters of water, then respectively will
10 grams of sodium acetate trihydrates, 4 grams of cetyl trimethylammonium bromides, 30 milliliters of ethylenediamine solutions are added in above-mentioned solution, stirring
It 15 minutes, is placed in reaction kettle, is reacted 12 hours under 210 degrees Celsius, be cooled to room temperature, after centrifuge washing, obtain pure phase
Ferric oxide powder.
(2) it prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
0.9 gram of end is dissolved in 500 milliliters of ethyl alcohol, is added 1.9 milliliters of tetraethoxysilanes, be added after stirring 4.5 hours 9 milliliters of ammonium hydroxide and
55 ml deionized waters stir 5.5 hours, and centrifugation is washed, after drying, then handled 6 hours under 450 degrees Celsius in tube furnace
Obtain di-iron trioxide/silicon dioxide nano composite material.
(3) it prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/silica obtained in step (2)
0.7 gram of nanocomposite is dissolved in 14 milliliters of water, and 0.5 gram of cetyl trimethylammonium bromide is added, after stirring 14 minutes, then
0.5 gram of resorcinol, 30 milliliters of dehydrated alcohols is added, 0.15 milliliter of ammonium hydroxide stirs in 45 C water baths and adds after forty minutes
Enter 0.06 milliliter of formaldehyde, after stirring in 9 hours, centrifuge washing uses sodium hydroxide after being then sintered 6 hours under 700 degrees Celsius
Solution etches one day, centrifuge washing was up to yolk shell structure di-iron trioxide/carbon nano-composite material.
(4) di-iron trioxide/carbon/trimanganese tetroxide nano composite material is prepared: the sample for taking 80 milligrams of steps (3) to prepare
Product are dissolved in 40 milliliters of water, and 0.15 gram of potassium permanganate and 60 milliliter 50% of manganese nitrate solution are separately added into above-mentioned solution, In
It is handled 80 minutes in 100 C water baths.It is sintered 80 minutes after centrifugal drying, then at 750 degrees c, finally obtains three oxygen
Change two iron/carbon/trimanganese tetroxide nano composite material.
It is shown in Figure 7, it is di-iron trioxide prepared by the present invention, di-iron trioxide/carbon composite and three oxidations
Two iron/carbon/mangano-manganic oxide composite material X-ray diffractogram.The diffraction maximum and standard powder of di-iron trioxide as seen from the figure
Diffraction card data library number (33-0664) is completely the same, and di-iron trioxide/carbon composite is by comparison in 20 to 25 degree
Between there is a wide and weak diffraction maximum to be the peak of carbonaceous material, di-iron trioxide/carbon composite and di-iron trioxide/
Carbon/mangano-manganic oxide composite material diffraction maximum contains standard di-iron trioxide and standard mangano-manganic oxide standard powder diffraction card
Wide and weak carbonaceous material diffraction maximum between all peaks on piece (24-0734) and 20 to 25 degree.
It is shown in Figure 8, it is the cyclic curve of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention
Figure, under 200 milliamperes of every gram of current densities, specific discharge capacity remains at 1056 every gram of milliampere hour after 100 circle circulations.
It is shown in Figure 9, it is the curve of double curvature of di-iron trioxide/carbon/mangano-manganic oxide composite material prepared by the present invention
Scheme, it can be seen that it is with excellent high rate performance in figure.
The foregoing is merely preferred embodiments of the invention, are not intended to restrict the invention, for the technology of this field
For personnel, the invention may be variously modified and varied.All any modification, equivalent substitution, improvement and etc. made for the present invention,
It should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of preparation method of lithium ion battery negative material, characterized by the following steps:
Step (1), hydro-thermal method prepare pure phase ferric oxide powder: 1-10 grams of ferric chloride hexahydrate is dissolved in 50-100 milliliters of water
In, then respectively by 5-15 grams of sodium acetate trihydrate, 1-5 grams of cetyl trimethylammonium bromide, 15-30 milliliters of ethylenediamine solutions add
Enter in above-mentioned solution, stirs 5-15 minutes, be placed in reaction kettle, reacted 8-15 hours under 150-220 degrees Celsius, be cooled to room
Temperature obtains the ferric oxide powder of pure phase after centrifuge washing；
Step (2) prepares di-iron trioxide/silicon dioxide nano composite material: taking ferric oxide powder obtained in step (1)
Last 0.5-1 grams is dissolved in 300-600 milliliters of ethyl alcohol, and 1.5-2.5 milliliters of tetraethoxysilanes are added, and stirring is added after 2-5 hours
5-15 milliliters of ammonium hydroxide and 30-60 ml deionized water stir 3-6 hours, after centrifugation, washing, drying, then the 200- in tube furnace
Di-iron trioxide/silicon dioxide nano composite material is handled 1-6 hours to obtain under 450 degrees Celsius；
Step (3) prepares di-iron trioxide/carbon nano-composite material: taking di-iron trioxide/titanium dioxide obtained in step (2)
0.2-0.7 grams of silicon nanocomposite is dissolved in 10-20 milliliters of water, and 0.1-0.5 grams of cetyl trimethylammonium bromide is added, stirs
After mixing 10-20 minutes, 0.1-0.5 grams of resorcinol, 10-30 milliliters of dehydrated alcohols, 0.05-0.15 milliliters of ammonium hydroxide, In are added
0.01-0.1 milliliters of formaldehyde are added after stirring 15-45 minutes in 20-45 C water bath, after stirring in 4-10 hours, centrifugation is washed
It washs, after being then sintered 1-6 hours under 450-700 degrees Celsius, is etched one day with sodium hydroxide solution, centrifuge washing is up to yolk
Shell structure di-iron trioxide/carbon nano-composite material；
Step (4) prepares di-iron trioxide/carbon/trimanganese tetroxide nano composite material: taking 40-100 milligrams of step (3) preparations
Sample be dissolved in 15-40 milliliters of water, the manganese nitrate solution of 0.05-0.15 grams of potassium permanganate and 40-80 milliliter 50% is added respectively
Enter above-mentioned solution, is handled 30-90 minutes in 50-100 C water bath；After centrifugal drying, then under 500-750 degrees Celsius
Sintering 30-90 minutes, finally obtains di-iron trioxide/carbon/trimanganese tetroxide nano composite material.
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