CN106450210A - Ferroferric oxide/graphite composite nano material, preparation method thereof and application thereof in lithium ion battery - Google Patents
Ferroferric oxide/graphite composite nano material, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a ferroferric oxide/graphite composite nano material, a preparation method thereof and application thereof in a lithium ion battery, belonging to the technical field of electrode materials of the lithium ion battery. The preparation method comprises the following steps: taking graphite and potassium ferrate as raw materials, adding zirconium balls, and using planetary ball mill balls at 300-500 rpmGrinding for 12-60 h, and then separating, filtering, washing and drying the product to obtain the ferroferric oxide/graphite composite nano material. The material is applied to the negative electrode of the lithium ion battery, has excellent electrical property and can reach the voltage of 200 mA g‑1At a current density of 970 mAh g after circulating for 100 circles‑1The reversible capacity of 250 cycles reaches 1132 mAh g‑1(ii) a At a high current density (1000 mA g)‑1) Under the condition of (1), the reversible capacity can still be kept at 650 mAh g after 200 cycles of circulation‑1Left and right.
Description
Technical field
The invention belongs to technical field of lithium ion battery electrode is and in particular to a kind of ferroso-ferric oxide/graphite is combined
Nano material and preparation method thereof and the application in lithium ion battery.
Background technology
Energy and environment have become as the 21 century most pressing problem, in the face of fossil energy exhaustion and environmental problem increasingly
Deteriorate, new forms of energy have progressively gone on the stage of history.Wherein, the secondary cell with lithium ion battery as representative receives extensively
Concern, and have been applied in a lot of fields.But current lithium ion battery still suffers from a lot of problems, the capacity of such as battery is low, circulation
Short life, high rate performance are good etc..For adapting to the demand in market, exploitation has the high power capacity, long-life, excellent high rate performance, honest and clean
The lithium ion battery negative material of valency environmental protection becomes crucial.Wherein, transition metal oxide is (as Fe2O3、Fe3O4、Mn3O4、MnO
Deng) and transient metal sulfide (as FeS2) there is higher theoretical capacity, it is expected to make up graphite (theoretical capacity 372mAh g-1)
As the deficiency of negative material capacity, have great application prospect.
Magnetic iron ore (Fe3O4) there is high theoretical capacity (926mAh g-1), earth rich reserves, cheap, no poison ring
The advantages of guarantor, be the potential advanced lithium ion battery negative material of a class.Generally believe Fe3O4As lithium ion battery negative
, in charge and discharge process, there is redox reaction in materialWith huge
Volume Changes, lead to material disintegrating, and then the cycle performance of battery and high rate performance are deteriorated.At present, existing a lot of work to change
The cyclical stability of kind battery and high rate performance, doping carbonaceous material (such as number of plies graphite flake, Graphene, reduction-oxidation graphite less
Alkene, porous carbon etc.) achieved with major progress.
There are a lot of article reports, all successfully synthesize Fe by the way of hydro-thermal3O4@GNs composite, effectively improves
Cyclical stability and high rate performance.Three-dimensional Fe as reports such as Li3O4/ G composite is in 92.5mA g-1Current density
Under, after circulation 50 circle, capacity remains to keep 609mAh g-1, significantly larger than simple Fe3O4As negative material (92.5mA g-1Electricity
Under current density, after circulation 50 circle, capacity only has 70mAh g-1).Jiang etc. also successfully synthesizes Fe3O4/ rGO composite, real
Show in 1.0A g-1Current density under, capacity is maintained at 1260mAh g-1.But hydro-thermal method there is also some unfavorable factors, system
Standby long, HTHP the condition of route is unfavorable for prepared by industrial mass production, has larger potential safety hazard simultaneously.
The present invention is intended to provide a kind of technique is easily simple, mild condition, the method that can achieve industrialization large-scale production,
By strong oxidizer potassium ferrate (K2FeO4) assist the mode of ball-milling technology to be successfully prepared ferroso-ferric oxide/few number of plies graphite
The composite nano materials of piece.Assembled by the use of the ferroso-ferric oxide/graphite composite nano materials of gained as ion cathode material lithium
Battery, under room temperature condition, in 200mA g-1Current density under, after circulation 100~250 circle capacity can be maintained at 970~
1132mAh g-1;And there is preferable high rate performance, 1A g-1Under current density, capacity has 656mAh g-1, in 2Ag-1Electricity
After circulation 100 circle under current density, capacity remains to be maintained at 504mAh g-1.Therefore, the present invention can provide a kind of process is simple, reality
Border is feasible, preparation method that is can industrializing large-scale production, has certain meaning and value.
Content of the invention
In order to overcome the deficiencies in the prior art, the primary and foremost purpose of the present invention is to provide a kind of ferroso-ferric oxide/graphite multiple
Close nano material.
Another object of the present invention is to providing above-mentioned ferroso-ferric oxide/low consumption of graphite composite nano materials, environmental protection, height
Effect and the method for the preparation that can be mass-produced.
It is still another object of the present invention to provide above-mentioned ferroso-ferric oxide/graphite composite nano materials are newly general as high-performance
Read the application of lithium ion battery negative material.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of ferroso-ferric oxide/graphite composite nano materials, including following preparation process:
(1) weigh graphite with potassium ferrate as raw material, be subsequently adding zirconium ball and be situated between as mill;
(2) utilize planetary ball mill ball milling;
(3) product separated, filter, wash, be dried, obtain ferroso-ferric oxide/graphite composite nano materials.
Preferably, the described graphite of step (1) is one or more of native graphite, electrographite and expanded graphite.
Preferably, the described zirconium ball of step (1) and the mass ratio of raw material are 8:1~30:1.
Preferably, rotating speed during step (2) described ball milling is 300~500rpm (note:Rpm represents rpm);Ball milling
Time be 12~60h.
The present invention prepares ferroso-ferric oxide/graphite composite nano materials using strong oxidizer auxiliary ball milling method, in the method,
The Main Function of ball milling:One is that the strong oxidation of Strong shear power by zirconium ball and potassium ferrate reduces the graphite number of plies, two
It is to make potassium ferrate be obtained ferroferric oxide nano granules by in-situ reducing, three is so that ferroso-ferric oxide is received by ball action
Rice grain is formed with graphite flake and is distributed homogeneous, constitutionally stable nano composite material.
In above-mentioned preparation method, the main purpose of washing is to wash the sylvite generating in course of reaction off.
A kind of ferroso-ferric oxide/graphite the composite nano materials being obtained by above-described preparation method.
Preferably, in described ferroso-ferric oxide/graphite composite nano materials, the content of graphite is 4wt%~35wt%.
It is further preferred that in described ferroso-ferric oxide/graphite composite nano materials graphite content be 6.8wt%~
25.4wt%.
Most preferably, in described ferroso-ferric oxide/graphite composite nano materials, the content of graphite is 18.2wt%.
A kind of above-described ferroso-ferric oxide/graphite composite nano materials answering as lithium ion battery negative material
With.
The process of described application is:Will be equal with carbon black, PVDF mixed grinding for ferroso-ferric oxide/graphite composite nano materials
Even, it is subsequently adding NMP slurrying, is coated on Copper Foil, after being dried, obtain lithium ion battery negative.
Preferably, described application process is:By ferroso-ferric oxide/graphite composite nano materials, PVDF (Kynoar)
With carbon black mixed grinding uniformly, add 1ml NMP (1-METHYLPYRROLIDONE) to continue to grind 0.5h, obtained slurry uniformly applies
Cloth, on Copper Foil, makes electrode after 12h is dried, using lithium piece as electrode group is dressed up with CR2016 type button cell.
Compared with prior art, the invention has the advantages that and beneficial effect:
(1) present invention adopts strong oxidizer to assist ball-milling method, one-step synthesis ferroso-ferric oxide/graphite composite nano materials
And successfully it is applied to lithium ion battery negative material.In mechanical milling process ferroferric oxide nano granules formed and with peel off
Graphite flake combine to form be evenly distributed, constitutionally stable ferroso-ferric oxide/graphite composite.Compound few number of plies graphite flake strengthens
The electric conductivity of material, shortens the passage of charge carrier migration, improves the high rate performance of battery;Meanwhile, graphite flake can be effectively
Suppression Volume Changes in charge and discharge process for the ferroferric oxide nano granules, enhance the structural stability of material, thus changing
The cycle performance of kind battery.
(2) the raw material potassium ferrate (K used by the present invention2FeO4) and graphite is all cheap, environmental protection, be easy to get, simultaneously using dry grinding
Ball-milling technology, process is simple, pollution be few, and can realize large batch of producing preparation.
(3) present invention is using the Fe with high theoretical capacity3O4As active material, multiple to it using few number of plies graphite flake
Close specific capacity, cyclical stability and the high rate performance being conducive to improving material.
(4) present invention can realize the four of different loads amount by controlling the ratio of reaction raw materials potassium ferrate and graphite
Fe 3 O/graphite composite nano materials.
(5) ferroso-ferric oxide of the present invention/graphite composite nano materials be used for lithium ion battery negative material when have good
Good cycle performance:Described composite nano materials when content of graphite be 6.8~18.2wt% when, at normal temperatures, current density
For 200mA g-1, after circulation 50~100 circle, capacity is 683~970mAh g-1.It can be seen that the lithium-ion negative pole material of present invention preparation
Material cycle performance preferably, is conducive to improving the service life of battery.
(6) when the ferroso-ferric oxide/graphite composite nano materials of the present invention are used for lithium ion battery negative material, have
Excellent high rate performance;When content of graphite is 6.8~18.2wt%, current density is 1000mA g-1, capacity can be maintained at
468~656mAh g-1.It can be seen that the lithium ion battery negative material of present invention preparation is still suitable under high current density, be lithium from
Use under high-power for the sub- battery provides safeguard.
Brief description
Fig. 1 is 200mA g for the embodiment of the present invention 3 gained ferroso-ferric oxide/graphite composite nano materials in current density-1
Charging and discharging curve figure when lower circulation the 1st circle, the 2nd circle and the 50th circle.
Fig. 2 is 200mA g for the embodiment of the present invention 3 gained ferroso-ferric oxide/graphite composite nano materials in current density-1
The charge-discharge performance figure of lower circulation 100 circle.
Fig. 3 is the TEM figure of the embodiment of the present invention 3 gained ferroso-ferric oxide/graphite composite nano materials.
Fig. 4 is the Raman figure of the embodiment of the present invention 3 gained ferroso-ferric oxide/graphite composite nano materials and native graphite.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
Weigh 7.0g potassium ferrate, 3.0g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 60h at 500 rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025gPVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 2
Weigh 8.0g potassium ferrate, 2.0g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 3
Weigh 8.5g potassium ferrate, 1.5g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
The present embodiment gained ferroso-ferric oxide/graphite composite nano materials are 200mA g in current density-1Lower circulation the 1st
Charging and discharging curve figure when circle, the 2nd circle and the 50th circle is as shown in figure 1, be 200mA g in current density-1What lower circulation 100 was enclosed fills
Discharge cycles performance map is as shown in Figure 2.
Embodiment 4
Weigh 9.0g potassium ferrate, 1.0g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 5
Weigh 9.5g potassium ferrate, 0.5g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 6
Weigh 9.6g potassium ferrate, 0.4g graphite, 250g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 7
Weigh 9.0g potassium ferrate, 1.0g graphite, 200g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h under 400rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 8
Weigh 9.0g potassium ferrate, 1.0g graphite, 300g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 48h at 300 rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Embodiment 9
Weigh 9.0g potassium ferrate, 1.0g graphite, 100g zirconium ball (mill is situated between), add in ball grinder, hand operated mixing is uniform, so
Utilize planetary ball mill ball milling 12h at 500 rpm afterwards, product, through filtering, washes with water, then in 60 in thermostatic drying chamber
12h is dried at DEG C, last grind into powder, obtain ferroso-ferric oxide/graphite composite nano materials.
By 0.200g ferroso-ferric oxide/graphite composite nano materials, 0.025g PVDF (Kynoar) and 0.025g carbon
Black mixed grinding uniformly, adds 1ml NMP (1-METHYLPYRROLIDONE) and continues to grind 0.5h, obtained slurry is uniformly coated on
On Copper Foil, after 12h is dried, make electrode, using lithium piece as electrode group is dressed up with CR2016 type button cell, carry out electrochemistry
Performance test.
Performance test:
Material use X-ray diffraction technology (XRD) of above-described embodiment preparation, Raman spectrum (Raman Spectra), sweep
Retouch electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) as characterization method, it is formed, pattern, particle diameter
And content of graphite is analyzed.
The TEM figure of the embodiment of the present invention 3 gained ferroso-ferric oxide/graphite composite nano materials, Raman figure such as Fig. 3, Fig. 4
Shown.Nano particle size is 10~20nm as seen from Figure 3;From fig. 4, it can be seen that the D peak of embodiment 3 is remarkably reinforced, indicate former
Work stone ink is sheared stripping, and the degree of disorder increases.The TEM figure of other embodiments gained ferroso-ferric oxide/graphite composite nano materials,
Raman schemes as Fig. 3, Fig. 4.
The battery of above-described embodiment preparation is after shelving 12h, soft using cell tester (the new prestige in Shenzhen) and BTS7.5.4
Part, test temperature is room temperature, and current density is 50mA g-1~5000mA g-1In the case of, constant current charge-discharge is carried out to it
(discharge cut-off voltage is 0.01V, and charging voltage is 3V), the cycle performance of test battery and high rate performance.The electrical property of sample
Refer to table 1.Using electrochemical workstation (CHI600E, Shanghai occasion China), it is circulated with volt-ampere (CV) and ac impedance measurement.
Table 1
The present invention has prepared ferroso-ferric oxide/graphite composite nano materials using potassium ferrate auxiliary ball milling method, and passes through
Change content of graphite and ratio of grinding media to material comes cycle performance and the high rate performance of research material.By comparing embodiment 1~6, find to work as
Ratio of grinding media to material is definite value (25:1) when, mass content of graphite is 6.2%~18.2% interval, and the cyclical stability of material contains with graphite
Amount increases and strengthens;When content reaches 25.4%, the capacity of battery reduces again, is shown to be the theoretical capacity institute low by graphite itself
Lead to.So, compound thin layer graphite piece serves the effect of buffers active component ferroso-ferric oxide volumetric expansion, considers
The protective effect of graphite flake and the low theoretical capacity of itself, the mineral carbon load amount of optimum selecting 18.2%.By comparing enforcement
Example 4,7~9, when raw material forms constant, change ratio of grinding media to material, it can be found that when ratio of grinding media to material is 25:When 1, material has more excellent
Cycle performance and high rate performance.Compared with prior art, the present invention successfully synthesizes ferroso-ferric oxide/stone using ball-milling method one step
Black composite nano materials, have that process is simple, raw material be cheap and easy to get, low consumption environmental protection, can to industrialize large-scale production preparation etc. all
Many advantages, have good application prospect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ferroso-ferric oxide/graphite composite nano materials is it is characterised in that include following preparation process:
(1)Weigh graphite with potassium ferrate as raw material, be subsequently adding zirconium ball and be situated between as mill;
(2)Using planetary ball mill ball milling;
(3)Product is separated, filter, wash, be dried, obtain ferroso-ferric oxide/graphite composite nano materials.
2. preparation method according to claim 1 is it is characterised in that step(1)Described graphite is native graphite, artificial stone
One or more of ink and expanded graphite.
3. preparation method according to claim 1 is it is characterised in that step(1)Described zirconium ball with the mass ratio of raw material is
8:1~30:1.
4. preparation method according to claim 1 is it is characterised in that step(2)Rotating speed during described ball milling be 300 ~
500rpm;The time of ball milling is 12 ~ 60h.
5. a kind of ferroso-ferric oxide/graphite composite nano materials that the preparation method described in any one of claim 1-4 is obtained.
6. a kind of ferroso-ferric oxide/graphite composite nano materials according to claim 5 are it is characterised in that described four oxygen
The content changing graphite in three-iron/graphite composite nano materials is 4wt% ~ 35wt%.
7. a kind of ferroso-ferric oxide/graphite composite nano materials according to claim 6 are it is characterised in that described four oxygen
The content changing graphite in three-iron/graphite composite nano materials is 6.8wt% ~ 25.4wt%.
8. a kind of ferroso-ferric oxide/graphite composite nano materials according to claim 7 are it is characterised in that described four oxygen
The content changing graphite in three-iron/graphite composite nano materials is 18.2wt%.
9. a kind of ferroso-ferric oxide/graphite composite nano materials described in claim 5 are as lithium ion battery negative material
Application.
10. application according to claim 9 is it is characterised in that the process of described application is:By ferroso-ferric oxide/graphite
Composite nano materials with carbon black, PVDF mixed grinding uniformly, are subsequently adding NMP slurrying, are coated on Copper Foil, obtain lithium after being dried
Ion battery negative pole.
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CN108726576A (en) * | 2018-06-01 | 2018-11-02 | 东莞理工学院 | Carbonization-activation oxidation is continuous to prepare porous charcoal/Fe3O4Method |
CN109961966A (en) * | 2017-12-25 | 2019-07-02 | 南京大学 | Peanut shell porous carbon/ferroso-ferric oxide combination electrode material preparation method |
CN111554963A (en) * | 2019-02-12 | 2020-08-18 | 成都佰思格科技有限公司 | Lithium ion battery and preparation method thereof |
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CN107611365A (en) * | 2017-07-27 | 2018-01-19 | 华南理工大学 | Graphene and ferroferric oxide double-coated nano-silicon composite material, preparation method thereof and application thereof in lithium ion battery |
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CN109961966A (en) * | 2017-12-25 | 2019-07-02 | 南京大学 | Peanut shell porous carbon/ferroso-ferric oxide combination electrode material preparation method |
CN109961966B (en) * | 2017-12-25 | 2021-04-06 | 南京大学 | Preparation method of porous carbon/ferroferric oxide composite electrode material of peanut shell |
CN108336330A (en) * | 2018-01-08 | 2018-07-27 | 东莞市凯金新能源科技股份有限公司 | Load the expanded graphite negative material and preparation method thereof of willow leaf shape ferroso-ferric oxide |
CN108726576A (en) * | 2018-06-01 | 2018-11-02 | 东莞理工学院 | Carbonization-activation oxidation is continuous to prepare porous charcoal/Fe3O4Method |
CN108726576B (en) * | 2018-06-01 | 2019-08-23 | 东莞理工学院 | The continuous preparation porous charcoal/Fe of carbonization-activation oxidation3O4Method |
CN111554963A (en) * | 2019-02-12 | 2020-08-18 | 成都佰思格科技有限公司 | Lithium ion battery and preparation method thereof |
CN113666345A (en) * | 2021-09-02 | 2021-11-19 | 湖南伟方生命科技有限公司 | Preparation method and application of graphite oxide phase carbon nitride |
CN113666345B (en) * | 2021-09-02 | 2023-12-26 | 湖南伟方生命科技有限公司 | Preparation method and application of graphite oxide phase carbon nitride |
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