CN106099077B - Carbon/ferriferrous oxide composite material preparation method, lithium ion battery - Google Patents
Carbon/ferriferrous oxide composite material preparation method, lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of carbon/ferriferrous oxide composite material, comprising: mixes ferrous carbonate with larger molecular organics, the heating and calcining in protective atmosphere obtains carbon/ferriferrous oxide composite material.Compared with prior art, the present invention is using ferrous carbonate micron particles as raw material, it can decompose in subsequent high-temperature calcination and obtains the ferroso-ferric oxide of Nano grade, to obtain the micrometer structure of nano particle composition, so that charge/discharge capacity is higher than the particle of simple nanometer or micron level, structure is also more stable；And, carbon material, which is added, can be such that reactive nanoparticles ferroso-ferric oxide is connected each other by three-dimensional network carbon, it can be used as buffer body and supporter, the hard force that buffer substance volume change generates, maintain the basic configuration of substance, carbon material conductivity with higher simultaneously the, so that carbon/ferriferrous oxide composite material being prepared has the characteristics that high magnification, height ratio capacity, macrocyclic.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of preparations of carbon/ferriferrous oxide composite material
Method, lithium ion battery.
Background technique
New energy lithium ion battery is emerging energy, and to meet the needs of society is to high-energy-density lithium battery, people are positive
Explore the lithium cell negative pole material with high theoretical specific capacity.
The theoretical specific capacity of traditional lithium cell negative pole material graphite is 372mAh/g, and known lithium electricity positive electrode is (such as
LiFePO 4, lithium cobalt oxide etc.) specific capacity it is also limited (100-200mAh/g), be to adapt to people to the need of high-energy lithium battery
It asks, whole to improve battery performance, researcher explores and synthesize a series of alternative negative electrode materials, these materials have high
Theoretical specific capacity (500-1000mAh/g), the development of lithium electricity full battery has been driven with this, wherein great application potential is novel
Negative electrode material is transition metal oxide (MxOy, M=Fe, Co, Ni, Cu, Mn etc.).But due to material reaction mechanism, material
Material structure changes, such as Fe3O4In charge and discharge process, with the intercalation/deintercalation of lithium ion, oxide (Fe3O4) and metal
It is mutually converted between grain (Fe), therefore causes oxide structure unstable, the problems such as capacity sharp-decay, and this is also current sheet
Field technical staff's urgent problem.
Research shows that most effective, easy improved method is doping carbon material.But many work will all obtain at present
Lithium oxide material is directly mixed with carbon source, annealing.This approach belongs to that rigid carbon is compound, active material and carbon source it is mutual
Effect matter both is present on contact surface, when an electric current passes through it, internal active material be unable to get carbon material supporting role and
The transmitting of electronics.Zhang etc. passes through reduction Fe2O3Spindle prepares monodisperse carbon coated ferriferrous oxide nano particle, in electric current
When multiplying power is 460mA/g, specific capacity maintains 530mAh/g after circulation 80 times, and under the same conditions, without carbon-coated material
Material capacity only has 150mAh/g (Advanced Functional Materials, 2008,18,3941-3946).Zhou etc. will
On graphene carbon material load to ferroferric oxide nano granules, when current ratio is 1000mA/g, 200 capacity of circulating battery
It is positively retained at 550mAh/g (RSC Advances, 2011,1,782-791).Above-mentioned many research work are mainly concentrated in
Improve material conductivity, specific discharge capacity or reduce scantling the problems such as on, form materials synthesis route it is complex, produce
Measure situation low, at high cost；Discharge capacity early period of more work simultaneously is considerable, but follow-up study is insufficient.
The stability of transition metal oxide can be additionally improved by constructing micro-nano material, but most reports at present, need
To regulate and control by multistep, need to control ion concentration because constructing particular configuration, using special organic solvent etc., lead to Product yields
Less, cost increases；And pattern control controlled factordisease is more, vulnerable to temperature, concentration, pressure and other parameters influence, therefore this side
Method poor operability.If it is compound to carry out carbon again, process will increase, and oxide structure has basically formed at this time, in carbonisation
Carbon material is difficult inside uniformly penetrating to active particle.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of carbon/ferriferrous oxide composite material
Carbon/ferriferrous oxide composite material of preparation method, lithium ion battery, this method preparation has higher powerful electric conductivity
Energy.
The present invention provides a kind of preparation methods of carbon/ferriferrous oxide composite material, comprising:
Ferrous carbonate is mixed with larger molecular organics, it is multiple to obtain carbon/ferroso-ferric oxide for the heating and calcining in protective atmosphere
Condensation material.
Preferably, the ferrous carbonate is prepared in accordance with the following methods:
Ferrous salt, urea are mixed in water with carbonate, hydro-thermal reaction is carried out, obtains ferrous carbonate.
Preferably, the ferrous salt is ferrous sulfate and/or frerrous chloride；The carbonate is ammonium hydrogen carbonate.
Preferably, the molar ratio of carbanion is 1:1 in the ferrous salt ferrous ions, urea and carbonate:
(0.26~1.01).
Preferably, the temperature of the hydro-thermal reaction is 100 DEG C~120 DEG C；The time of the hydro-thermal reaction is 10~12h.
Preferably, the larger molecular organics are acetate fiber and/or sucrose.
Preferably, the mass ratio of the ferrous carbonate and larger molecular organics is (2~2.25): 1.
Preferably, the mixing specifically:
Ferrous carbonate, larger molecular organics and volatile solvent are subjected to ball milling mixing.
Preferably, the protective atmosphere is nitrogen and/or argon gas；The temperature of the calcining is 500 DEG C~550 DEG C；It is described
The time of calcining is 5~10h.
The present invention also provides a kind of lithium ion batteries, including carbon/ferriferrous oxide composite material.
The present invention provides a kind of preparation methods of carbon/ferriferrous oxide composite material, comprising: by ferrous carbonate and big point
Sub- organic matter mixing, the heating and calcining in protective atmosphere obtain carbon/ferriferrous oxide composite material.Compared with prior art, originally
Invention, as raw material, can decompose in subsequent high-temperature calcination using ferrous carbonate micron particles and obtain four oxygen of Nano grade
Change three-iron, so that the micrometer structure of nano particle composition is obtained, so that charge/discharge capacity is than simple nanometer or micron level
Particle wants high, and structure is also more stable；Also, carbon material, which is added, can make reactive nanoparticles ferroso-ferric oxide each other by three
The connection of network carbon is tieed up, can be used as buffer body and supporter, the hard force that buffer substance volume change generates maintains the basic structure of substance
Type, while carbon material conductivity with higher, so that the carbon/ferriferrous oxide composite material being prepared has high power
Rate, height ratio capacity, macrocyclic feature.
Detailed description of the invention
Fig. 1 provides carbon/ferriferrous oxide composite material preparation flow schematic diagram for the present invention；
Fig. 2 provides the connection schematic diagram of both ferroso-ferric oxide and carbon in carbon/ferriferrous oxide composite material for the present invention；
Fig. 3 is carbon provided by the invention/ferriferrous oxide composite material electron-transport schematic diagram；
Fig. 4 is the structural schematic diagram of lithium ion battery provided by the invention；
A is the stereoscan photograph of presoma ferrous carbonate obtained in the embodiment of the present invention 1 in Fig. 5；
B is carbon/ferriferrous oxide composite material stereoscan photograph obtained in the embodiment of the present invention 1 in Fig. 5；
C is carbon/ferriferrous oxide composite material stereoscan photograph obtained in the embodiment of the present invention 1 in Fig. 5；
D is carbon/ferriferrous oxide composite material transmission electron microscope photo obtained in the embodiment of the present invention 1 in Fig. 5；
Fig. 6 is the electricity that carbon/ferriferrous oxide composite material is 1000mA in current density obtained in the embodiment of the present invention 1
Pond cyclic specific capacity curve graph；
Fig. 7 is the electricity that carbon/ferriferrous oxide composite material is 2000mA in current density obtained in the embodiment of the present invention 1
Pond cyclic specific capacity curve graph.
Specific embodiment
The present invention provides a kind of preparation methods of carbon/ferriferrous oxide composite material, comprising: by ferrous carbonate and big point
Sub- organic matter mixing, the heating and calcining in protective atmosphere obtain carbon/ferriferrous oxide composite material.
The present invention is not particularly limited the source of all raw materials, for commercially available or self-control.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or battery field
The conventional purity used.
Wherein, the ferrous carbonate is preferably micron particles, more preferably follows the steps below preparation: will be ferrous
Salt, urea mix in water with carbonate, carry out hydro-thermal reaction, obtain ferrous carbonate.
The ferrous salt is the compound well known to those skilled in the art containing ferrous ion, has no special limit
It makes, is preferably ferrous sulfate and/or frerrous chloride in the present invention.
The carbonate is carbonate well known to those skilled in the art, has no special limitation, excellent in the present invention
It is selected as ammonium hydrogen carbonate.
Ferrous salt, urea are mixed in water with carbonate；Wherein, the ferrous salt ferrous ions, urea and carbonic acid
The molar ratio of carbanion is preferably 1:1:(0.26~1.01 in salt), more preferably 1:1:(0.38~0.63), most preferably
For 1:1:0.506；The molar concentration of mixed liquor ferrous ions is preferably 0.125~0.145mol/L after the mixing.Urea
Effect be the concentration of relation control ferrous ion and the growth of production die, it mainly plays the pattern of product in the present invention
Control action.
After mixing, hydro-thermal reaction is carried out, ferrous carbonate is obtained；The temperature of the hydro-thermal reaction is preferably 80 DEG C~150 DEG C,
More preferably 100 DEG C~130 DEG C, be further preferably 100 DEG C~120 DEG C, most preferably 120 DEG C；The time of the hydro-thermal reaction is excellent
It is selected as 10~12h, more preferably 11~12h, is further preferably 12h.
Ferrous carbonate is mixed with larger molecular organics；Wherein, the larger molecular organics are that those skilled in the art are ripe
That knows can be used as the larger molecular organics of carbon source, have no special limitation, in the present invention preferably cellulose acetate and/or
Sucrose, more preferably cellulose acetate or sucrose；Using larger molecular organics as carbon source, the carbon material that may make has height
Continuity, and the particle obtained just with ferrous carbonate pyrolytic matches, thus to electronics in battery charge and discharge process
Transmission and capacity embodiment play a key effect.The mass ratio of the ferrous carbonate and larger molecular organics is preferably (2~2.25):
1, more preferably (2~2.2): 1, it is further preferably (2~2.1): 1, most preferably 2:1.
In the present invention, the mixed method of ferrous carbonate and larger molecular organics is that method well known to those skilled in the art is
Can, special limitation is had no, ferrous carbonate, larger molecular organics and volatile solvent are preferably subjected to ball milling mixing；It is described
Volatile solvent is volatile organic solvent well known to those skilled in the art, has no special limitation, excellent in the present invention
It is selected as acetone and/or dehydrated alcohol, more preferably acetone or dehydrated alcohol；The preferred three of amount that the volatile solvent is added is mixed
Semi-liquid phase is synthesized, ferrous carbonate and larger molecular organics can be infiltrated；The time of the ball milling is preferably 5
~10h, more preferably 5~8h are further preferably 5~6h, most preferably 5h.
After mixing, the heating and calcining in protective atmosphere；The protective atmosphere is protection gas well known to those skilled in the art
Atmosphere has no special limitation, is preferably nitrogen and/or argon gas, more preferably nitrogen or argon gas in the present invention；The calcining
Temperature be preferably 500 DEG C~550 DEG C；In some embodiments provided by the invention, the temperature of the calcining is preferably 500
℃；In other embodiments provided by the invention, the temperature of the calcining is preferably 550 DEG C；The time of the calcining is preferred
It is further preferably 5~6h for 5~10h, more preferably 5~8h.Calcination process is ferrous carbonate pyrolytic and big in the present invention
Process molecular organic carbonization while carried out.
After cooling, carbon/ferriferrous oxide composite material can be obtained, preparation flow schematic diagram is as shown in Figure 1.
The present invention also provides a kind of carbon/ferriferrous oxide composite materials of above method preparation, consist of two parts,
The connection schematic diagram of ferroso-ferric oxide and carbon, the two is as shown in Figure 2；Wherein ferriferrous oxide particles are active material, three-dimensional carbon
The conductivity of composite material can be improved in matrix, also can be used as the structure of support substance stabilizing material.Three-dimensional carbon base body can be regarded as
One parent, active particle are uniformly distributed therein, and particle is connected by carbon phase each other.Carbon/ferroso-ferric oxide provided by the invention is multiple
Condensation material electron-transport schematic diagram is as shown in figure 3, when an electric current passes through it, three-dimensional carbon base body can be rapidly by electron-transport to activity
On particle, the electric conductivity of material is which thereby enhanced；When cycle charge-discharge, although active particle is changed into iron by ferroso-ferric oxide
Simple substance, material structure variation, but under the supporting role of three-dimensional carbon frame, active particle degree of grinding reduces, and microstructure obtains
With protection, thus battery cycle life significantly extends.
The present invention also provides a kind of lithium ion batteries, including above-mentioned carbon/ferriferrous oxide composite material.
The lithium ion battery is lithium ion battery structure well known to those skilled in the art, has no special limit
System.The anode of lithium ion battery is the compound containing lithium metal, generally lithium iron phosphate (such as LiFePO4 LiFePO4, phosphoric acid
Cobalt lithium LiCoO2Deng), cathode is preferably carbon/ferriferrous oxide composite material, uses organic solvent as electrolysis between positive and negative anodes
Matter.When charging the battery, it is decomposed on anode and generates lithium ion, lithium ion enters battery cathode by electrolyte, is embedded in
In the micropore of negative electrode material.(electric discharge is equivalent to) in the use process of battery, and the lithium ion in cathode micropore moves again
Return anode.The lithium ion for returning to anode is more, and discharge capacity is higher, and usually signified battery capacity is exactly discharge capacity.This
Sample, in battery charge and discharge process, lithium ion constantly makes little runs to and fro between positive and negative anodes, so lithium ion battery is also referred to as
Rocking chair type battery.
As shown in figure 4, anode of the compound containing lithium metal as battery, is connect by plus plate current-collecting body with anode,
Centre is the diaphragm of polymer, it separates positive electrode and negative electrode, but lithium ion Li+It can cannot be passed through by electronics e-, it is right
While the battery cathode being made of carbon/ferriferrous oxide composite material, is connected by the cathode of negative current collector and battery.Battery
It is the electrolyte of battery between upper and lower side, battery is by metal shell enclosed package.
In the present invention, the plus plate current-collecting body is collector well known to those skilled in the art, has no special limit
It makes, is preferably aluminium foil or carbon-coated aluminum foils in the present invention；The negative current collector is that collector well known to those skilled in the art is
Can, special limitation is had no, is preferably copper foil or painting carbon copper foil in the present invention.
Because aluminium embedding lithium of meeting under low potential, is unfit to do negative current collector；Copper can aoxidize under high potential, be unfit to do anode
Collector, but aluminium surface has passivation layer, therefore can be used as plus plate current-collecting body.Carbon-coated aluminum foils are to be led using functional coating to battery
It is a breakthrough technological innovation that electric substrate, which carries out surface treatment, and carbon-coated aluminum foils/copper foil is exactly by scattered conductive nano
Graphite and carbon coating grain uniformly, fine and smoothly are coated on aluminium foil/copper foil, it can provide splendid static conductive performance, collect and live
Property substance micro-current, so as to the contact resistance being greatly lowered between positive/negative material and afflux, and both can improve
Between adhesive ability, the usage amount of binder can be reduced, and then generate the overall performance of battery and be obviously improved coating point
Aqueous (aqua system) and oiliness (organic solvent system) two types.
Lithium ion Li of the lithium ion battery in charging, in anode+It is migrated by membrane for polymer to cathode；It was discharging
Cheng Zhong, the lithium ion Li in cathode+It is migrated by diaphragm to anode.Lithium ion battery be exactly because of lithium ion in charge and discharge back and forth
Migration and name.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
0.995g FeCl2·4H2O, 0.3g urea (CO (NH2)2) and 0.2g NH4HCO3It is dissolved into 40ml water, heats
To 120 DEG C, hydro-thermal reaction 12h, obtains and collect presoma ferrous carbonate.
0.3460g presoma ferrous carbonate is mixed with 0.1730g cellulose acetate [mass ratio 2:1], 2ml second is added
After ball milling 5h, compounding substances are dried for alcohol, under protection of argon gas, are heated to 500 DEG C, are kept 5h, natural cooling obtains carbon/tetra-
Fe 3 O composite material.
Carbon/ferriferrous oxide composite material obtained in embodiment 1 is detected using surface analysis instrument, obtains it
Specific surface area is 67.296m2/g；Pore-size distribution has larger distribution at 3.8 and 5nm two, illustrates that material is mesoporous material, favorably
In storage of the electrolyte inside active material and quickly transmission.
It is compound to presoma ferrous carbonate obtained in embodiment 1 and carbon/ferroso-ferric oxide using scanning electron microscope
Material is analyzed, its stereoscan photograph is obtained, as shown in figure 5, wherein figure a is that the scanning electron microscope of presoma ferrous carbonate is shone
Piece；B and c is carbon/ferriferrous oxide composite material stereoscan photograph.
Carbon/ferriferrous oxide composite material obtained in embodiment 1 is analyzed using transmission electron microscope, is obtained
Its transmission electron microscope photo is as shown in d in Fig. 5.
It forms carbon/ferriferrous oxide composite material obtained in embodiment 1 as negative electrode material into lithium battery, positive material
Material is metal lithium sheet, and diaphragm is 2400 models, material is polyolefin porous membrane, and electrolyte is 1.0mol/L LiPF6It is organic molten
Liquid, solvent are ethylene carbonate (EC)/diethyl carbonate (DEC), volume ratio 1:1.It is right using blue electrical measurement test system (Wuhan)
The electrochemistry of obtained lithium battery can be carried out detection, obtain charging and discharging curve and cycle life test, as shown in Figures 6 and 7.
By Fig. 6 and Fig. 7 it is found that when current density is 1000mA/g and 2000mA/g, after circulating battery 1000 times, specific discharge capacity
Reach 750mAh/g, is 81.17% (theoretical specific capacity of ferroso-ferric oxide is 924mAh/g) of theoretical specific capacity, illustrates three
Under the action of tieing up carbon base body, the lithium electrical testing of product is had excellent performance, and is had extended cycle life.
Embodiment 2
1.4g FeSO4·7H2O, 0.3g CO (NH2)2With 0.2g NH4HCO3It is dissolved into 40ml water, is heated to 120 DEG C,
Hydro-thermal reaction 10h obtains and collects presoma ferrous carbonate, and subsequent experimental is the same as embodiment 1.
Surface analysis has been carried out to carbon/ferriferrous oxide composite material obtained in embodiment 2, the results showed that, product
With 67.3m2The specific surface area of/g, pore-size distribution are typical mesoporous material, are conducive to electrolyte in activity in 4~5nm
The storage of material internal and quickly transmission.
Embodiment 3
0.995g FeCl2·4H2O, 0.3g CO (NH2)2With 0.2g NH4HCO3It is dissolved into 40ml water, is heated to 120
DEG C, hydro-thermal reaction 12h is obtained and is collected presoma ferrous carbonate.
0.30g presoma ferrous carbonate is mixed with 0.15g sucrose (mass ratio 2:1), 2ml ethyl alcohol, ball milling 5h is added
Afterwards, compounding substances are dried, under protection of argon gas, is heated to 550 DEG C, keeps 6h, natural cooling obtains carbon/ferroso-ferric oxide
Composite material.Subsequent experimental is the same as example 1.
Surface analysis has been carried out to carbon/ferriferrous oxide composite material obtained in embodiment 3, the results showed that, product
With 67.3m2The specific surface area of/g, pore-size distribution are typical mesoporous material, are conducive to electrolyte in activity in 4~5nm
The storage of material internal and quickly transmission.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (8)
1. a kind of preparation method of carbon/ferriferrous oxide composite material characterized by comprising
Ferrous carbonate micron particles are mixed, the heating and calcining in protective atmosphere with larger molecular organics, obtains carbon/tetra- oxidations three
Iron composite material；
The larger molecular organics are acetate fiber and/or sucrose；
The mass ratio of the ferrous carbonate and larger molecular organics is (2~2.25): 1；
The temperature of the calcining is 500 DEG C~550 DEG C；The time of the calcining is 5~10h.
2. preparation method according to claim 1, which is characterized in that the ferrous carbonate is prepared in accordance with the following methods:
Ferrous salt, urea are mixed in water with carbonate, hydro-thermal reaction is carried out, obtains ferrous carbonate.
3. preparation method according to claim 2, which is characterized in that the ferrous salt is ferrous sulfate and/or protochloride
Iron；The carbonate is ammonium hydrogen carbonate.
4. preparation method according to claim 2, which is characterized in that the ferrous salt ferrous ions, urea and carbonic acid
The molar ratio of carbanion is 1:1:(0.26~1.01 in salt).
5. preparation method according to claim 2, which is characterized in that the temperature of the hydro-thermal reaction is 100 DEG C~120
℃；The time of the hydro-thermal reaction is 10~12h.
6. preparation method according to claim 1, which is characterized in that the mixing specifically:
Ferrous carbonate, larger molecular organics and volatile solvent are subjected to ball milling mixing.
7. preparation method according to claim 1, which is characterized in that the protective atmosphere is nitrogen and/or argon gas.
8. a kind of lithium ion battery, which is characterized in that including carbon/ferroso-ferric oxide prepared by claim 1~7 any one
Composite material.
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| CN107665979A (en) * | 2017-08-24 | 2018-02-06 | 浙江工业大学 | A kind of cathode of lithium battery prepared based on iron cement and preparation method thereof |
| CN108306001B (en) * | 2018-01-08 | 2021-04-16 | 北京科技大学 | Lithium ion battery cathode material Fe3O4Preparation method of/N-C |
| CN109935756B (en) * | 2018-11-27 | 2022-05-13 | 万向一二三股份公司 | Preparation method of lithium ion battery composite diaphragm and lithium ion battery containing composite diaphragm |
| CN110492079A (en) * | 2019-08-26 | 2019-11-22 | 东北大学 | A kind of preparation method and application of sheet ferroso-ferric oxide negative electrode material |
| CN115321508A (en) * | 2022-09-06 | 2022-11-11 | 国网内蒙古东部电力有限公司通辽供电公司 | Positive porous lithium iron phosphate material for low-temperature battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| CN103413941A (en) * | 2013-07-23 | 2013-11-27 | 华南农业大学 | Lithium ion battery cathode material and preparation method thereof |
| CN103840132A (en) * | 2014-03-03 | 2014-06-04 | 湖南雅城新材料发展有限公司 | Ferrous carbonate/graphene composite material and preparation method and applications thereof |
-
2016
- 2016-08-18 CN CN201610702533.3A patent/CN106099077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| CN103413941A (en) * | 2013-07-23 | 2013-11-27 | 华南农业大学 | Lithium ion battery cathode material and preparation method thereof |
| CN103840132A (en) * | 2014-03-03 | 2014-06-04 | 湖南雅城新材料发展有限公司 | Ferrous carbonate/graphene composite material and preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and lithium storage performances of mesoporous Fe3O4@C microcapsules;S. M. Yuan et al;《ACS applied materials & interfaces》;20110301;第3卷(第3期);第705页左栏第1段-第706页左栏第1段 * |
| Thermal formation of porous Fe3O4/C microspheres and the lithium storage performance;Liu Rui et al;《Journal of Alloys and Compounds》;20140605;第597卷;第30页左栏第1段-第31页右栏第2段 * |
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