CN106129361B - 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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- CN106129361B CN106129361B CN201610589288.XA CN201610589288A CN106129361B CN 106129361 B CN106129361 B CN 106129361B CN 201610589288 A CN201610589288 A CN 201610589288A CN 106129361 B CN106129361 B CN 106129361B
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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 present invention provides a kind of lithium ion battery anode active material and preparation method, which includes SnFe2O4Metal composite oxide and redox graphene.The preparation of the active material cathode of lithium battery the specific steps are：By the compound of iron and tin with molar ratio for 2:1 ratio is added in anhydrous alcohol or ketone, and graphene oxide is then added, and ultrasound makes evenly dispersed.Make anode with platinized platinum, copper foil does cathode, using two-probe method under suitable voltage and sedimentation time, the compound of tin iron/graphene oxide is deposited at merits and demerits on copper foil, be carbonized appropriate time at suitable temperature, in nitrogen atmosphere, the SnFe prepared2O4/ redox graphene (rGO) is without adding adhesive, directly as lithium cell negative pole material.There is good lithium electrical property by the lithium battery that the negative material assembles.This method is easy to operate, at low cost, and purity is high, and prepared lithium battery is had excellent performance.
Description
Technical field：
The present invention relates to field of batteries, more particularly to a kind of lithium ion battery anode active material and preparation method, cathode
Pole piece and lithium ion battery.
Background technology
Lithium ion battery is because of its high-energy density, high power density, high specific capacitance and can be miniaturized to as weight
The energy wanted is widely used in mobile phone, palm PC, electric vehicle etc..But since the application range of nowadays lithium ion battery is more next
It is wider, to the energy density of lithium ion battery, specific capacitance, power density etc. require it is higher and higher, it is traditional using graphite as lithium
The lithium battery theory specific capacitance of electric cathode only has 372mAh/g, can no longer meet application demand, therefore develop novel cathode material
Material is very necessary.
Transition metal oxide is because the studied application of its high theoretical specific capacitance is used as lithium cell negative pole material.Dioxy
The high 782mA h/g of its theoretical specific capacitance of change tin, are used as lithium cell negative pole material.Patent CN200910306128.X is provided
A kind of preparation of the stannic oxide nanometer hollow ball being made of nanometer rods and its application in lithium battery, the SnO2Nano-hollow
Ball is made of nanometer rods, and operating method is simple, at low cost, and purity is high, as lithium cell negative pole material have very high 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 so as to cause the lithiums electrical property rapid attenuation such as specific capacitance, cyclical stability.In order to solve
Problems, researchers are compound with carbon-based material in transition metal oxide, on the one hand carbon-based material can increase electrode slice
Electric conductivity, on the other hand can inhibit transiting metal oxidation in charge and discharge process as the load layer of transition metal material
Object structure caused by due to volume expansion is destroyed.
In recent years, binary metal oxide material of numerous researchers based on exploitation is using carbon-based material is negative as lithium electricity
A large amount of work has been done in terms of the material of pole, and has achieved significant achievement.Such as CoMn2O4@carbon nanotubes, ZnMn2O4@carbon is received
Meter Wei Qiu, ZnFe2O4@carbon nano rods, NiCo2O4The carbon-based binary metal oxide such as@carbon nanosheets is as lithium electric material.Patent
CN201410521942.4 can deposit the hydroxide of one layer of nano level tin using technique is co-deposited on carbon source material surface
Or the hydroxide or subcarbonate of subcarbonate and cobalt, after hydrogen reducing, the deposit on carbon source surface is transformed into tin
Cobalt alloy adds amorphous carbon after carbon nanotubes is added and coats to form nucleocapsid as lithium cell negative pole active material.But
It is that lithium battery first charge discharge efficiency made of the material is low, first discharge specific capacity is less than 500mA h/g.Cyclical stability is poor, 100 times
Specific capacity after cycle is only the 60% of initial specific capacities.
Based on described above, if a kind of composite reactive material of carbon-based tin and other metal composite metal oxides can be invented
Material, it is high to use it as made from lithium cell negative pole material lithium battery first discharge specific capacity, good rate capability, good cycling stability,
Secondly the preparation process of active material is simple, economical, environmentally friendly, then this preparation method will be highly beneficial to this field.
Invention content：
Based on this, it is necessary to provide a kind of tin iron metal composite oxide/redox graphene SnFe2O4It is prepared by@rGO
Method.
A kind of SnFe2O4The preparation method of@rGO, it is characterised in that prepared, specifically included as follows using electrochemical deposition method
Step：
Ferric chemical combination is with stannous chloride or its hydrate with Fe:The molar ratio 2 of Sn:1 ratio is dissolved in anhydrous alcohol
In class or organic solvent of ketone, graphene oxide dry in right amount, ultrasonic disperse is added.Using platinized platinum as anode, copper foil conduct
Cathode, constant voltage dc source carry out electro-deposition experiment as power supply under constant pressure.After sedimentation experiment, deposition piece is often depressed
It carries out carbonization treatment after drying process under suitable temperature and time in inert gas, prepares the lithium without any binder
Ion battery negative electrode active material tin iron compound oxide/redox graphene composite material SnFe2O4@rGO。
Further, which is characterized in that the ferric compound is ferric nitrate or nitric hydrate iron, ferric trichloride or water
Ferric trichloride is closed, ferric sulfate or ferric sulfate hydrate etc. can be dissolved in ferric compound and its hydration of anhydrous alcohols or ketone
Object.As solvent, anhydrous alcohols, any one of ketone.Graphene oxide GO is with respect to stannous chloride or its hydration
The additive amount of amount of substance is 1000：(30-8000), 0.5~500 μm of size.
Further, which is characterized in that the electro-deposition voltage 20~200V, 3~30min of sedimentation time.At constant pressure and dry
The temperature range of reason is 50~150 DEG C, drying time is 1~for 24 hours.
Further, which is characterized in that carbonization treatment in the atmosphere of inert gases, atmosphere of inert gases are nitrogen, argon gas,
Helium etc. not with the gas that is carbonized object and reacts.400 DEG C~1000 DEG C of carburizing temperature, carbonization time 1~for 24 hours.
In conclusion to prepare SnFe2O4There are following three points difficult points for@rGO compounds：1, the compound of selected iron must
Must be stable ferric iron compound, tin is bivalent compound, and must be dissolved in selected alcohols or ketones solvent；2, anti-
Answer middle addition ferric iron compound and divalent tin compound necessarily molar ratio be 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
It can decompose or other side reactions.
Description of the drawings：
Fig. 1 is SnFe2O4The flow chart of the preparation method of@rGO；
Fig. 2 is electro-deposition schematic diagram；
Fig. 3 is the SnFe prepared by example 12O4The photo figure of@rGO；
Fig. 4 is SnFe2O4The SEM of@rGO schemes；
Fig. 5 is SnFe2O4The TEM of@rGO schemes；
Specific implementation mode：
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Specific implementation mode be described in detail.Many details are elaborated in the following description in order to fully understand this hair
It is bright.But the present invention be without can also implement in the case of these details, those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
It is the SnFe of an embodiment as shown in Figure 12O4The preparation method of@rGO, includes the following steps：
(1) as shown in Fig. 2, being that constant pressure electrodeposition process prepares SnFe2O4The schematic diagram of@rGO.Power supply is constant-voltage DC source,
Anode is platinum electrode, and cathode is copper foil, pole plate spacing 1cm.
(2) electrolyte is anhydrous alcohols or ketone.
(3) ferric compound is ferric nitrate or nitric hydrate iron, ferric trichloride or iron chloride hexahydrate, ferric sulfate or
Ferric sulfate hydrate etc. can be dissolved in the ferric compound and its hydrate of anhydrous alcohols or ketone
(4) ferric chemical combination and stannous chloride or its hydrate are with Fe:The molar ratio 2 of Sn:1 initial proportion is dissolved in electricity
It solves in liquid.
(5) 10~1000mg of additive amount of GO, 0.5~500 μm of size.
(6) 20~200V of electro-deposition voltage, 3~30min of sedimentation time.The temperature range of constant pressure and dry processing is 50~
150 DEG C, drying time is 1~for 24 hours.
(7) tin iron compound@GO carbonization treatments in atmosphere of inert gases prepared by electro-deposition, atmosphere of inert gases are
Nitrogen, argon gas, helium etc. not with the gas that is carbonized object and reacts.400 DEG C~1000 DEG C of carburizing temperature, carbonization time 1~for 24 hours.
Embodiment 1：
GO, Fe(NO3)39H2O 202mg and two hydrated stannous chloride 56.5mg that 100mg sizes are 500 μm are added to
In 100mL ethanol solutions, ultrasonic 0.5h.Electro-deposition experiment is carried out under conditions of constant pressure using two-probe method, anode is adopted
With platinum electrode, cathode uses copper foil, deposition voltage 100V, sedimentation time 10min.After electro-deposition, deposition there is into Xi Tiehua
The copper foil for closing object@GO is removed from cathode, and 80 DEG C of air dryings handle 15h.Then the carbonization treatment at 500 DEG C in nitrogen atmosphere
6h.Through prepared by 1 preparation process of example be exactly any binder of object the SnFe using copper foil as collector2O4@rGO lithium electricity
Pond negative electrode active material.
The present invention is directly by the prepared SnFe without any binder2O4@rGO cathode of lithium battery active materials are cut into directly
The disk of diameter 1.2mm uses lithium piece, uses the LiPF of 1mol/L as lithium cell negative pole, anode6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is assembled into CR2016 type simulated batteries as electrolyte, microporous polypropylene membrane as diaphragm.
Fig. 3 is the SnFe after carbonization treatment in implementing 12O4@rGO cathode of lithium battery active materials.It can be seen from the figure that
Without using any binder, by the method for electro-deposition, the SnFe that is obtained after carbonization treatment2O4@rGO live
Property material well-proportioned can be supported on copper foil.
Fig. 4, Fig. 5 are to implement SnFe prepared in 1 respectively2O4The SEM of@rGO cathode of lithium battery active materials, TEM Electronic Speculum
Scheme, as can be seen from Figure prepared SnFe2O4Uniform load is in rGO on pieces, prepared SnFe2O4Cubic type, the length of side is presented
Size is in the range of 10-70nm.
The present invention carries out cycle performance and the high rate performance test of lithium battery, charge and discharge using the current density of 100mA/g
Voltage is limited in 0~3V.At room temperature, the electricity of battery is tested using Wuhan Lan electricity Electronics Co., Ltd.s LAND battery test systems
Chemical property.The SnFe prepared by invention example 12O4@rGO active materials are as the discharge capacity for the first time of cathode of lithium battery
843.6mA h/g, first charge-discharge efficiency 88.7%.SnFe2O4The specific capacitance of lithium battery prepared by@rGO active materials has
Good self-propagation trend, capacity retention ratio has 130.7% after recycling 200 times, has good cycle performance of battery.
The SnFe prepared by invention example 12O4High rate performance test curve of the@rGO active materials as cathode of lithium battery.
At room temperature, the chemical property of battery is tested using Wuhan Lan electricity Electronics Co., Ltd.s LAND battery test systems.Voltage model
0~3V is enclosed, the current density of high rate performance test is 100mA/g, 200mA/g, 500mA/g, 1000mA/g, 2000mA/ respectively
G, 4000mA/g, 100mA/g, corresponding electric discharge specific capacitance is 615.4mA h/g respectively under respective current density,
573.6mA h/g,531.7mA h/g,485.3mA h/g,446.4mA h/g,397.8mA h/g,703.7mA h/g.
Lithium electricity is 615.4mA h/g than constant volume after preceding ten cycles under the current density of 100mA/g, and when by different current densities
Current density turns again to 100mA/g after test, and battery ratio appearance increases to 703.7mA h/g, apparent self-propagation occurs
Phenomenon.Simultaneously under high current density 4000mA/g, specific capacitance also has 397.8mA h/g, is compared to the current density of 100mA/g
Under specific capacitance still have 58.1% reservation, illustrate by the SnFe prepared by example 12O4@rGO active materials are as lithium cell negative pole
There is good high rate performance.
Embodiment 2：
GO, Iron(III) chloride hexahydrate 90.2mg and two hydrated stannous chloride 37.3mg that 1000mg sizes are 500nm are added
Enter into 100mL anhydrous isopropanol solutions, ultrasonic 0.5h.Electro-deposition experiment is carried out under conditions of constant pressure using two-probe method,
Anode uses platinum electrode, cathode to use copper foil, deposition voltage 20V, sedimentation time 30min.After electro-deposition, deposition there is into tin
The copper foil of iron compound@GO is removed from cathode, and 150 DEG C of air dryings handle 3h.Then it is carbonized at 1000 DEG C in argon atmosphere
Handle 1h.Through prepared by 2 preparation process of example be exactly any binder of object the SnFe using copper foil as collector2O4@rGO
Cathode of lithium battery active material.
The present invention is directly by the prepared SnFe without any binder2O4@rGO cathode of lithium battery active materials are cut into directly
The disk of diameter 1.2mm uses lithium piece, uses the LiPF of 1mol/L as lithium cell negative pole, anode6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is assembled into CR2016 type simulated batteries as electrolyte, microporous polypropylene membrane as diaphragm.
SnFe2O4The discharge capacity for the first time of lithium battery prepared by@rGO active materials is 848.3mA h/g, SnFe2O4@rGO active materials
The specific capacitance of the lithium battery of preparation has good self-propagation trend, and capacity retention ratio has 84.3% after recycling 110 times, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after preceding ten cycles under the current density of 100mA/g
It is 632.4mA h/g than constant volume, and current density turns again to 100mA/g, battery ratio after being tested by different current densities
Capacitance increases to 697.7mA h/g, apparent self-propagation phenomenon occurs.Simultaneously under high current density 4000mA/g, specific capacitance
Also 403.8mA h/g, the specific capacitance being compared under the current density of 100mA/g still have 63.8% reservation, illustrate by real
SnFe prepared by example 22O4@rGO active materials have good high rate performance as lithium cell negative pole.
Embodiment 3：
By 10mg sizes be 50 μm of GO, ferric sulfate 266.7mg and two hydrated stannous chloride 75.3mg be added to 100mL without
In water acetone soln, ultrasonic 0.5h.Electro-deposition experiment is carried out under conditions of constant pressure using two-probe method, anode is using platinum electricity
Pole, cathode use copper foil, deposition voltage 200V, sedimentation time 3min.After electro-deposition, deposition there are into tin iron compound@GO
Copper foil removed from cathode, the processing of 50 DEG C of air dryings is for 24 hours.Then carbonization treatment is for 24 hours at 400 DEG C in helium atmosphere.Through reality
That prepared by 3 preparation process of example is exactly the SnFe using copper foil as collector of any binder of object2O4@rGO cathode of lithium battery is lived
Property material.
The present invention is directly by the prepared SnFe without any binder2O4@rGO cathode of lithium battery active materials are cut into directly
The disk of diameter 1.2mm uses lithium piece, uses the LiPF of 1mol/L as lithium cell negative pole, anode6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is assembled into CR2016 type simulated batteries as electrolyte, microporous polypropylene membrane as diaphragm.
SnFe2O4The discharge capacity for the first time of lithium battery prepared by@rGO active materials is 798.3mA h/g, SnFe2O4@rGO active materials
The specific capacitance of the lithium battery of preparation has good self-propagation trend, and capacity retention ratio has 86.3% after recycling 110 times, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after preceding ten cycles under the current density of 100mA/g
It is 602.4mA h/g than constant volume, and current density turns again to 100mA/g, battery ratio after being tested by different current densities
Capacitance increases to 707.7mA h/g, apparent self-propagation phenomenon occurs.Simultaneously under high current density 4000mA/g, specific capacitance
Also 393.8mA h/g, the specific capacitance being compared under the current density of 100mA/g still have 65.4% reservation, illustrate by real
SnFe prepared by example 32O4@rGO active materials have good high rate performance as lithium cell negative pole.
Embodiment 4：
GO, Fe(NO3)39H2O 242mg and two hydrated stannous chloride 113mg that 500mg sizes are 150 μm are added to
In the N-Methyl pyrrolidone solution of 100mL, ultrasonic 0.5h.Electro-deposition reality is carried out under conditions of constant pressure using two-probe method
It tests, anode uses platinum electrode, cathode to use copper foil, deposition voltage 60V, sedimentation time 15min.After electro-deposition, it will deposit
There is the copper foil of tin iron compound@GO to be removed from cathode, 100 DEG C of air dryings handle 12h.Then in helium atmosphere at 600 DEG C
Carbonization treatment 5h.Through prepared by 4 preparation process of example be exactly any binder of object the SnFe using copper foil as collector2O4@
RGO cathode of lithium battery active materials.
The present invention is directly by the prepared SnFe without any binder2O4@rGO cathode of lithium battery active materials are cut into directly
The disk of diameter 1.2mm uses lithium piece, uses the LiPF of 1mol/L as lithium cell negative pole, anode6Three component mixed solvents are as EC:
DMC:EMC=1:1:1 mixed liquor is assembled into CR2016 type simulated batteries as electrolyte, microporous polypropylene membrane as diaphragm.
SnFe2O4The discharge capacity for the first time of lithium battery prepared by@rGO active materials is 724.3mA h/g, SnFe2O4@rGO active materials
The specific capacitance of the lithium battery of preparation has good self-propagation trend, and capacity retention ratio has 85.6% after recycling 110 times, has very
Good cycle performance of battery.High rate performance test result finds out lithium electricity after preceding ten cycles under the current density of 100mA/g
It is 612.4mA h/g than constant volume, and current density turns again to 100mA/g, battery ratio after being tested by different current densities
Capacitance increases to 713.7mA h/g, apparent self-propagation phenomenon occurs.Simultaneously under high current density 4000mA/g, specific capacitance
Also 381.3mA h/g, the specific capacitance being compared under the current density of 100mA/g still have 62.3% reservation, illustrate by real
SnFe prepared by example 42O4@rGO active materials have good high rate performance as lithium cell negative pole.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore 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, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (4)
1. a kind of preparation method of battery cathode active material, which is characterized in that include the following steps：
Ferric compound is with stannous chloride or its hydrate with Fe:The molar ratio 2 of Sn:1 ratio be dissolved in any type without
In the alcohols or organic solvent of ketone of water, graphene oxide, ultrasonic disperse is added；Using platinized platinum as anode, copper foil as cathode,
Constant voltage dc source carries out electro-deposition experiment as power supply under constant pressure；After deposition test, deposits and be dried under piece normal pressure
It carries out carbonization treatment again in inert gas afterwards, it is multiple to prepare the lithium ion battery anode active material tin iron without any binder
Close oxide-redox graphene composite material SnFe2O4@rGO。
2. preparation method according to claim 1, which is characterized in that the ferric compound be can be dissolved in it is anhydrous
The ferric compound and its hydrate of alcohols or ketone；Graphene oxide with respect to stannous chloride or its be hydrated amount of substance and add
Dosage is 1000：(30-8000), 0.5~500 μm of size.
3. preparation method according to claim 1, which is characterized in that 20~200V of the electro-deposition voltage, sedimentation time 3
The temperature range of~30min, constant pressure and dry processing are 50~150 DEG C, drying time is 3~for 24 hours.
4. preparation method according to claim 1, which is characterized in that carbonization treatment in the atmosphere of inert gases, inertia
Atmosphere is nitrogen, argon gas or helium, 400 DEG C~1000 DEG C of carburizing temperature, carbonization time 1~for 24 hours.
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| 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 |
| CN107256951B (en) * | 2017-06-08 | 2019-12-10 | 陕西科技大学 | CoO/reduced graphene oxide composite negative electrode material and preparation method thereof |
| CN109449379B (en) * | 2018-09-12 | 2021-05-11 | 华南师范大学 | Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof |
| CN111029563B (en) * | 2019-12-10 | 2022-11-29 | 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 |
| CN112331815B (en) * | 2020-11-04 | 2021-09-10 | 四川大学 | Iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and preparation method thereof |
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