CN106129361A - A kind of lithium ion battery anode active material and preparation method - Google Patents
A kind of lithium ion battery anode active material and preparation method Download PDFInfo
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- CN106129361A CN106129361A CN201610589288.XA CN201610589288A CN106129361A CN 106129361 A CN106129361 A CN 106129361A CN 201610589288 A CN201610589288 A CN 201610589288A CN 106129361 A CN106129361 A CN 106129361A
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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
- H01M4/364—Composites as mixtures
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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
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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
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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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- 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 invention provides a kind of lithium ion battery anode active material and preparation method, this active material includes SnFe2O4Metal composite oxide and redox graphene.The preparation of this active material cathode of lithium battery concretely comprises the following steps: the compound of ferrum and the stannum ratio with mol ratio as 2:1 joined in anhydrous alcohol or ketone, is subsequently adding graphene oxide, ultrasonic make dispersed.Making positive pole with platinized platinum, Copper Foil does negative pole, uses two-probe method under suitable voltage and sedimentation time, becomes merits and demerits to be deposited on Copper Foil the complex of stannum ferrum/graphene oxide, carbonization appropriate time at suitable temperature, in nitrogen atmosphere, the SnFe prepared2O4/ redox graphene (rGO) is without adding binding agent, directly as lithium cell negative pole material.The lithium battery assembled by this negative material has good lithium electrical property.The method is easy and simple to handle, low cost, and purity is high, prepared lithium battery excellent performance.
Description
Technical field:
The present invention relates to field of batteries, particularly to a kind of lithium ion battery anode active material and preparation method, negative pole
Pole piece and lithium ion battery.
Background technology
Lithium ion battery because its high-energy-density, high power density, high specific capacitance and can be miniaturized thus as weight
The energy wanted is widely used in mobile phone, palm PC, electric motor car etc..But owing to the range of application of nowadays lithium ion battery is more come
The widest, to lithium ion battery energy density, ratio electric capacity, power density etc. requires more and more higher, traditional using graphite as lithium
The lithium battery theory of electricity negative pole only has 372mAh/g than electric capacity, cannot meet application demand, therefore develop novel negative pole material
Expect the most necessary.
Transition metal oxide is applied as lithium cell negative pole material because its high theory is more studied than electric capacity.Dioxy
Change the 782mA h/g that its theory of stannum is higher than electric capacity, be used as lithium cell negative pole material.Patent CN200910306128.X provides
The preparation of a kind of stannic oxide nanometer hollow ball being made up of nanometer rods and the application in lithium battery, this SnO2Nano-hollow
Ball is made up of nanometer rods, and operational approach is simple, low cost, and purity is high, as lithium cell negative pole material have the highest specific capacity and
Cycle performance.But simple transition metal oxide is because of low electric conductivity and excessive volume in lithium electricity charge and discharge process
Expansion rate and cause material structure destroy thus cause than the lithium electrical property rapid attenuation such as electric capacity, cyclical stability.In order to solve
Problems, researchers are combined with carbon-based material at transition metal oxide, and on the one hand carbon-based material can increase electrode slice
Electric conductivity, on the other hand can suppress transiting metal oxidation in charge and discharge process as the load layer of transition metal material
The structural deterioration that thing causes because of volumetric expansion.
In recent years, numerous researcheres are born as lithium electricity using the binary metal oxide material based on carbon-based material in exploitation
Pole material aspect has done substantial amounts of work, and achieves significant achievement.Such as CoMn2O4@CNT, ZnMn2O4@carbon is received
Meter Wei Qiu, ZnFe2O4@carbon nano rod, NiCo2O4The carbon back binary metal oxides such as@carbon nanosheet are as lithium electric material.Patent
CN201410521942.4 uses codeposition technique can deposit the hydroxide of one layer of nano level stannum on carbon source material surface
Or subcarbonate and the hydroxide of cobalt or subcarbonate, after hydrogen reducing, the deposit on carbon source surface is transformed into stannum
Cobalt alloy, adds amorphous carbon cladding after adding CNT and forms nucleocapsid structure as lithium cell negative pole active material.But
Being that the lithium battery efficiency first that this material is made is low, first discharge specific capacity is less than 500mA h/g.Cyclical stability is poor, 100 times
Specific capacity after circulation is only the 60% of initial specific capacities.
Based on mentioned above, if the composite reactive material of a kind of carbon back stannum and other metal composite metal-oxides can be invented
Material, uses it as the prepared lithium battery first discharge specific capacity of lithium cell negative pole material high, good rate capability, good cycling stability,
Secondly the preparation process of active material is simple, economy, environmental protection, then this preparation method will be highly beneficial to this area.
Summary of the invention:
Based on this, it is necessary to provide a kind of stannum ferrum metal composite oxide/redox graphene SnFe2O4Prepared by@rGO
Method.
A kind of SnFe2O4The preparation method of@rGO, it is characterised in that use electrochemical deposition method to prepare, specifically include as follows
Step:
Ferric chemical combination is dissolved in anhydrous alcohol with stannous chloride or its hydrate with the ratio of mol ratio 2:1 of Fe:Sn
In class or organic solvent of ketone, add the appropriate graphene oxide being dried, ultrasonic disperse.Using platinized platinum as anode, Copper Foil conduct
Negative electrode, constant voltage dc source is as carrying out electro-deposition experiment under power supply, constant voltage.After sedimentation experiment terminates, deposition sheet is often depressed
In noble gas, under suitable temperature and time, carry out carbonization treatment after dried, prepare the lithium without any binding agent
Ion battery negative active core-shell material stannum iron compound oxide/redox graphene composite SnFe2O4@rGO。
Further, it is characterised in that described ferric compound is ferric nitrate or nitric hydrate ferrum, ferric chloride or water
Closing ferric chloride, iron sulfate or ferric sulfate hydrate etc. can be dissolved in anhydrous alcohols or the ferric compound of ketone and hydration thereof
Thing.As solvent, anhydrous alcohols, any one of ketone.Graphene oxide GO is relative to stannous chloride or its hydration
The addition of material amount is 1000:(30-8000), size 0.5~500 μm.
Further, it is characterised in that described electro-deposition voltage 20~200V, sedimentation time 3~30min.At constant pressure and dry
The temperature range of reason is 50~150 DEG C, and drying time is 1~24h.
Further, it is characterised in that carbonization treatment in described atmosphere of inert gases, atmosphere of inert gases is nitrogen, argon,
Helium etc. not be carbonized the gas that thing reacts.Carburizing temperature 400 DEG C~1000 DEG C, carbonization time 1~24h.
In sum, SnFe to be prepared2O4There is following three points difficult point in@rGO complex: 1, the compound of selected ferrum must
Must be stable ferric iron compound, stannum be bivalent compound, and must be dissolved in selected alcohols or ketones solvent;2, anti-
Ferric iron compound and the Bivalent Tin compound necessarily mol ratio added in should are n (Fe): n (Sn)=2:1;The selected alcohol of reaction
Class, ketones solvent are required anhydrous, and can dissolve ferric iron and stannous compound, and during electro-deposition is tested not
Can decompose or other side reactions.
Accompanying drawing illustrates:
Fig. 1 is SnFe2O4The flow chart of the preparation method of@rGO;
Fig. 2 is electro-deposition schematic diagram;
Fig. 3 is the SnFe by example 1 preparation2O4The photo figure of@rGO;
Fig. 4 is SnFe2O4The SEM figure of@rGO;
Fig. 5 is SnFe2O4The TEM figure of@rGO;
Detailed description of the invention:
Understandable, below in conjunction with the accompanying drawings to the present invention for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
Detailed description of the invention be described in detail.Elaborate a lot of detail in the following description so that fully understanding this
Bright.But the present invention also can implement in the case of not having these details, those skilled in the art can be without prejudice to this
Doing similar improvement in the case of bright intension, therefore the present invention is not limited by following public being embodied as.
It is the SnFe of an embodiment as shown in Figure 12O4The preparation method of@rGO, comprises the steps:
(1) as in figure 2 it is shown, be that constant voltage electrodeposition process prepares SnFe2O4The schematic diagram [email protected] supply is constant-voltage DC source,
Anode is platinum electrode, and negative electrode is Copper Foil, polar plate spacing 1cm.
(2) electrolyte is anhydrous alcohols or ketone.
(3) ferric compound is ferric nitrate or nitric hydrate ferrum, ferric chloride or iron chloride hexahydrate, iron sulfate or
Ferric sulfate hydrates etc. can be dissolved in anhydrous alcohols or the ferric compound of ketone and hydrate thereof.
(4) ferric chemical combination is dissolved in electricity with stannous chloride or its hydrate with the initial proportion of mol ratio 2:1 of Fe:Sn
Solve in liquid.
(5) addition 10~1000mg of GO, size 0.5~500 μm.
(6) electro-deposition voltage 20~200V, sedimentation time 3~30min.Constant pressure and dry process temperature range be 50~
150 DEG C, drying time is 1~24h.
(7) the stannum iron compound@GO carbonization treatment in atmosphere of inert gases prepared by electro-deposition, atmosphere of inert gases is
Nitrogen, argon, helium etc. not be carbonized the gas that thing reacts.Carburizing temperature 400 DEG C~1000 DEG C, carbonization time 1~24h.
Embodiment 1:
The GO of 100mg a size of 500 μm, Fe(NO3)39H2O 202mg and two hydrated stannous chloride 56.5mg are joined
In 100mL ethanol solution, ultrasonic 0.5h.Using two-probe method to carry out electro-deposition experiment under conditions of constant voltage, anode is adopted
With platinum electrode, negative electrode uses Copper Foil, deposition voltage 100V, sedimentation time 10min.After electro-deposition terminates, deposition there is Xi Tiehua
The Copper Foil of compound@GO takes off from negative electrode, and 80 DEG C of normal temperature drying process 15h.Then carbonization treatment at 500 DEG C in nitrogen atmosphere
6h.Through being exactly the SnFe using Copper Foil as collector of any binding agent of thing prepared by example 1 preparation process2O4@rGO lithium electricity
Pond negative active core-shell material.
The present invention is directly by the prepared SnFe without any binding agent2O4@rGO cathode of lithium battery active material is cut into directly
The disk of footpath 1.2mm uses lithium sheet as lithium cell negative pole, positive pole, uses the LiPF of 1mol/L6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is as electrolyte, and microporous polypropylene membrane, as barrier film, is assembled into CR2016 type simulated battery.
Fig. 3 is to implement in 1, the SnFe after carbonization treatment2O4@rGO cathode of lithium battery active material.It can be seen that
In the case of not using any binding agent, by the method for electro-deposition, the SnFe obtained after carbonization treatment2O4@rGO lives
Property material can well-proportioned be supported on Copper Foil.
Fig. 4, Fig. 5 are to implement SnFe prepared in 1 respectively2O4SEM, the TEM Electronic Speculum of@rGO cathode of lithium battery active material
Figure, as can be seen from Figure prepared SnFe2O4Uniform load on rGO sheet, prepared SnFe2O4Present cubic type, the length of side
Size is in the range of 10-70nm.
The present invention uses the electric current density of 100mA/g to carry out cycle performance and high rate performance test, the discharge and recharge of lithium battery
Voltage is limited in 0~3V.At room temperature, the electricity of Wuhan Lan electricity Electronics Co., Ltd. LAND battery test system test battery is used
Chemical property.SnFe by invention example 1 preparation2O4@rGO active material as the discharge capacity first of cathode of lithium battery is
843.6mA h/g, first charge-discharge efficiency is 88.7%.SnFe2O4The ratio electric capacity of lithium battery prepared by@rGO active material has
Well self-propagation trend, after circulating 200 times, capability retention has 130.7%, has good cycle performance of battery.
SnFe by invention example 1 preparation2O4@rGO active material is as the high rate performance test curve of cathode of lithium battery.
At room temperature, the chemical property of Wuhan Lan electricity Electronics Co., Ltd. LAND battery test system test battery is used.Voltage model
Enclosing 0~3V, the electric current density of high rate performance test is 100mA/g respectively, 200mA/g, 500mA/g, 1000mA/g, 2000mA/
G, 4000mA/g, 100mA/g, electric discharge corresponding under respective electric current density is 615.4mA h/g than electric capacity respectively,
573.6mA h/g,531.7mA h/g,485.3mA h/g,446.4mA h/g,397.8mA h/g,703.7mA h/g.?
After front ten circulations under the electric current density of 100mA/g, lithium electricity is 615.4mA h/g than constant volume, and when through different electric current densities
Test after current density turns again to 100mA/g, and battery ratio appearance increases to 703.7mA h/g, self-propagation clearly occurs
Phenomenon.Simultaneously under high current density 4000mA/g, also have 397.8mA h/g than electric capacity, be compared to the electric current density of 100mA/g
Under ratio electric capacity still have 58.1% reservation, the SnFe as prepared by example 1 is described2O4@rGO active material is as lithium cell negative pole
There is good high rate performance.
Embodiment 2:
The GO of 1000mg a size of 500nm, Iron(III) chloride hexahydrate 90.2mg and two hydrated stannous chloride 37.3mg are added
Enter in 100mL anhydrous isopropanol solution, ultrasonic 0.5h.Two-probe method is used to carry out electro-deposition experiment under conditions of constant voltage,
Anode uses platinum electrode, and negative electrode uses Copper Foil, deposition voltage 20V, sedimentation time 30min.After electro-deposition terminates, deposition there is stannum
The Copper Foil of iron compound@GO takes off from negative electrode, and 150 DEG C of normal temperature drying process 3h.Then carbonization at 1000 DEG C in argon atmosphere
Process 1h.Through being exactly the SnFe using Copper Foil as collector of any binding agent of thing prepared by example 2 preparation process2O4@rGO
Cathode of lithium battery active material.
The present invention is directly by the prepared SnFe without any binding agent2O4@rGO cathode of lithium battery active material is cut into directly
The disk of footpath 1.2mm uses lithium sheet as lithium cell negative pole, positive pole, uses the LiPF of 1mol/L6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is as electrolyte, and microporous polypropylene membrane, as barrier film, is assembled into CR2016 type simulated battery.
SnFe2O4The discharge capacity first of lithium battery prepared by@rGO active material is 848.3mA h/g, SnFe2O4@rGO active material
The ratio electric capacity of the lithium battery of preparation has good self-propagation trend, and after circulating 110 times, capability retention has 84.3%, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after front ten circulations under the electric current density of 100mA/g
It is 632.4mA h/g than constant volume, and when turning again to 100mA/g, battery ratio through different electric current density test after current density
Electric capacity increases to 697.7mA h/g, self-propagation phenomenon clearly occurs.Simultaneously under high current density 4000mA/g, compare electric capacity
Also having 403.8mA h/g, the ratio electric capacity being compared under the electric current density of 100mA/g still has the reservation of 63.8%, illustrates by real
SnFe prepared by example 22O4@rGO active material has good high rate performance as lithium cell negative pole.
Embodiment 3:
The GO of 10mg a size of 50 μm, iron sulfate 266.7mg and two hydrated stannous chloride 75.3mg are joined 100mL without
In water acetone soln, ultrasonic 0.5h.Using two-probe method to carry out electro-deposition experiment under conditions of constant voltage, anode uses platinum electricity
Pole, negative electrode uses Copper Foil, deposition voltage 200V, sedimentation time 3min.After electro-deposition terminates, deposition is had stannum iron compound@GO
Copper Foil take off from negative electrode, 50 DEG C of normal temperature drying process 24h.Then carbonization treatment 24h at 400 DEG C in helium atmosphere.Through reality
Prepared by example 3 preparation process is exactly the SnFe using Copper Foil as collector of any binding agent of thing2O4@rGO cathode of lithium battery is lived
Property material.
The present invention is directly by the prepared SnFe without any binding agent2O4@rGO cathode of lithium battery active material is cut into directly
The disk of footpath 1.2mm uses lithium sheet as lithium cell negative pole, positive pole, uses the LiPF of 1mol/L6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is as electrolyte, and microporous polypropylene membrane, as barrier film, is assembled into CR2016 type simulated battery.
SnFe2O4The discharge capacity first of lithium battery prepared by@rGO active material is 798.3mA h/g, SnFe2O4@rGO active material
The ratio electric capacity of the lithium battery of preparation has good self-propagation trend, and after circulating 110 times, capability retention has 86.3%, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after front ten circulations under the electric current density of 100mA/g
It is 602.4mA h/g than constant volume, and when turning again to 100mA/g, battery ratio through different electric current density test after current density
Electric capacity increases to 707.7mA h/g, self-propagation phenomenon clearly occurs.Simultaneously under high current density 4000mA/g, compare electric capacity
Also having 393.8mA h/g, the ratio electric capacity being compared under the electric current density of 100mA/g still has the reservation of 65.4%, illustrates by real
SnFe prepared by example 32O4@rGO active material has good high rate performance as lithium cell negative pole.
Embodiment 4:
The GO of 500mg a size of 150 μm, Fe(NO3)39H2O 242mg and two hydrated stannous chloride 113mg are joined
In the N-Methyl pyrrolidone solution of 100mL, ultrasonic 0.5h.Two-probe method is used to carry out electro-deposition under conditions of constant voltage real
Testing, anode uses platinum electrode, and negative electrode uses Copper Foil, deposition voltage 60V, sedimentation time 15min.After electro-deposition terminates, will deposition
The Copper Foil having stannum iron compound@GO takes off from negative electrode, and 100 DEG C of normal temperature drying process 12h.Then in helium atmosphere at 600 DEG C
Carbonization treatment 5h.Through being exactly the SnFe using Copper Foil as collector of any binding agent of thing prepared by example 4 preparation process2O4@
RGO cathode of lithium battery active material.
The present invention is directly by the prepared SnFe without any binding agent2O4@rGO cathode of lithium battery active material is cut into directly
The disk of footpath 1.2mm uses lithium sheet as lithium cell negative pole, positive pole, uses the LiPF of 1mol/L6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is as electrolyte, and microporous polypropylene membrane, as barrier film, is assembled into CR2016 type simulated battery.
SnFe2O4The discharge capacity first of lithium battery prepared by@rGO active material is 724.3mA h/g, SnFe2O4@rGO active material
The ratio electric capacity of the lithium battery of preparation has good self-propagation trend, and after circulating 110 times, capability retention has 85.6%, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after front ten circulations under the electric current density of 100mA/g
It is 612.4mA h/g than constant volume, and when turning again to 100mA/g, battery ratio through different electric current density test after current density
Electric capacity increases to 713.7mA h/g, self-propagation phenomenon clearly occurs.Simultaneously under high current density 4000mA/g, compare electric capacity
Also having 381.3mA h/g, the ratio electric capacity being compared under the electric current density of 100mA/g still has the reservation of 62.3%, illustrates by real
SnFe prepared by example 42O4@rGO active material has good high rate performance as lithium cell negative pole.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (4)
1. the preparation method of a battery cathode active material, it is characterised in that comprise the steps:
Ferric compound is dissolved in any nothing with stannous chloride or its hydrate with the ratio of mol ratio 2:1 of Fe:Sn
In the alcohols of water or organic solvent of ketone, add graphene oxide, ultrasonic disperse.Using platinized platinum as anode, Copper Foil as negative electrode,
Constant voltage dc source is as carrying out electro-deposition experiment under power supply, constant voltage.After deposition test terminates, dried under deposition sheet normal pressure
After in noble gas, carrying out carbonization treatment, prepare the lithium ion battery anode active material stannum ferrum without any binding agent multiple
Close oxide-redox graphene composite SnFe2O4@rGO。
Preparation method the most according to claim 1, it is characterised in that described ferric compound is ferric nitrate or hydration
Ferric nitrate, ferric chloride or iron chloride hexahydrate, iron sulfate or ferric sulfate hydrate can be dissolved in the trivalent of anhydrous alcohols or ketone
The compound of ferrum and hydrate thereof;Graphene oxide is 1000:(30-relative to the addition of stannous chloride or its hydrate quality
8000), size 0.5~500 μm.
Preparation method the most according to claim 1, it is characterised in that described electro-deposition voltage 20~200V, sedimentation time 3
~30min, the temperature range that constant pressure and dry processes is 50~150 DEG C, and drying time is 3~24h.
Preparation method the most according to claim 1, it is characterised in that carbonization treatment in described atmosphere of inert gases, inertia
Atmosphere is nitrogen, argon or helium, carburizing temperature 400 DEG C~1000 DEG C, carbonization time 1~24h.
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CN107256951A (en) * | 2017-06-08 | 2017-10-17 | 陕西科技大学 | A kind of CoO/ redox graphenes cathode composite materials and preparation method thereof |
CN107452939A (en) * | 2017-01-04 | 2017-12-08 | 中国地质大学(北京) | A kind of high power capacity flexible lithium ion battery negative material and preparation method thereof |
CN109449379A (en) * | 2018-09-12 | 2019-03-08 | 华南师范大学 | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof |
CN111029563A (en) * | 2019-12-10 | 2020-04-17 | 河南创力新能源科技股份有限公司 | Preparation method of alkaline secondary battery iron negative electrode material |
CN112331815A (en) * | 2020-11-04 | 2021-02-05 | 四川大学 | Three-dimensional micro-nano composite porous iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and one-step preparation method thereof |
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CN112331815A (en) * | 2020-11-04 | 2021-02-05 | 四川大学 | Three-dimensional micro-nano composite porous iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and one-step preparation method thereof |
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