CN110429259A - Catalytic type SnO2- Fe-C lithium ion battery negative material and its preparation method and application - Google Patents
Catalytic type SnO2- Fe-C lithium ion battery negative material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion, especially a kind of catalytic type SnO2- Fe-C lithium ion battery negative material and its preparation method and application including porous carbon matrix and is equably embedded in the SnO of porous carbon content2With Fe nano particle.Its pattern includes sheet or tufted；Having a size of 500nm~100 μm；SnO2It is 1~600nm with Fe nanoparticle size.Lithium ion battery negative material produced by the present invention has by porous carbon-based and be uniformly embedded in SnO therein2, Fe nano particle constitute porous SnO2- Fe-C nano composite structure.In 1A g‑1Discharge capacity is up to 1041.3mAh g respectively after recycling 200 times under current density‑1, 6A g‑1Discharge capacity is up to 820.0mAh g respectively after recycling 500 times under current density‑1.The equipment that preparation method uses is simple, and process is easy to control, obtained negative electrode material high magnification capacity with higher and cyclical stability.
Description
Technical field
The present invention relates to technical field of lithium ion, specific field is a kind of lithium ion battery negative material and its preparation
Method.
Background technique
In recent years, can charging-discharging lithium ion battery rely on their high-energy density, long circulation life and environment friendly
As potential electric/hybrid automobile and the energy stores and conversion equipment of intermittent renewable energy.In order to full
The foot demand more more and more urgent to low expense and high performance lithium ion battery, extensive work person are dedicated to high electrochemical activity
With the development of reversible electrode material.
In this case, SnO2By its high theoretical capacity (1494mAhg-1) and it is appropriate to lithium current potential (≈ 1.0V
vs Li/Li+) attract the concern of researcher.SnO2Negative electrode material stores Li by two steps, and the first step is conversion reaction
(SnO2+Li+→Sn+Li2O 731mAh g) is generated-1Capacity, second step be alloying reaction (Sn+4.4Li+→Li4.4Sn it) produces
Raw 763mAh g-1Capacity.
But SnO2The realization of all told needs to solve the problems, such as three: 1) SnO2Huge volume change during lithiumation
Lead to the reduction in capacity attenuation and service life；2)SnO2Low electric conductivity；3) low coulombic efficiency caused by irreversible conversion reaction.
Therefore, researcher is solved the above problems using number of ways trial.Such as patent CN201110101600.3 is adopted
With congruent melting solvent type ionic liquid low temperature preparation nanocrystalline structure SnO2Lithium ion battery negative material.Patent
CN201811105582.4 provide a kind of three-dimensional sea urchin/porous composite construction lithium ion battery copper/copper oxide/stannic oxide/
Carbon anode is made of the cycle performance for improving negative electrode of lithium ion battery three-D nano-porous copper, oxidation copper film, stannic oxide and carbon
And high rate performance.As can be seen that current technology is often faced with or composite construction is complicated, preparation flow is cumbersome or still
Do not solve SnO fundamentally so2The problem of material low-rate capacity and low circulation service life.
Recent studies suggest that metal nanoparticle (Fe, Mn, Co, Ni etc.) goes back metal oxidation in electrochemical reaction process
Former and SEI film reversible transition has catalysis.Obviously, if being able to achieve SnO2(providing high capacity), metal nano are urged
Change material (catalysis enhancing SnO2Reactivity improves electrode conductivity and adjusts SEI film thickness) and porous carbon substrate (guarantee height
Conductivity, Li diffusion coefficient and structural stability) it is reasonable compound, will be for high performance low temperature lithium ion battery negative material
Research and development provide a new approaches.Therefore, the present invention is by being based on a kind of solvent thermal process, using alcohol type organic to metal ion
Chelation and subsequent simple thermal treatment complete SnO2, Fe, C it is effective compound, without complicated material selection and
Factor regulation, is beneficial to design next-generation high rate lithium ionic cell cathode material.
Summary of the invention
The purpose of the present invention is to provide a kind of catalytic type SnO2- Fe-C lithium ion battery negative material and preparation method thereof
And application, SnO can be realized by the regulation of preparation method easily2- Fe-C composite material appearance and size and wherein SnO2It is received with Fe
The control of rice grain composite microstructure, and then obtain the promotion of composite negative pole material high power charging-discharging capacity and cycle life.
Especially, Fe and SnO2Nano particle is uniform and stable compound in carbon matrix, on the one hand ensure that Fe to SnO2Electrochemical process
Situ catalytic is carried out, another aspect carbon matrix avoids Fe and SnO2Reunion of the nano particle in electrochemistry cyclic process or
Separation, to enhance SnO2Charge/discharge capacity of-Fe-C the composite lithium ion battery cathode material under high current densities
And cyclical stability.Method according to the present invention has the improvement of other lithium ion battery negative material performances with raising
Important directive significance.
Lithium ion battery negative material produced by the present invention has by porous carbon-based and be uniformly embedded in SnO therein2、
The porous SnO that Fe nano particle is constituted2- Fe-C nano composite structure.In 1A g-1It discharges and holds after being recycled 200 times under current density
Amount is up to 1041.3mAh g respectively-1, 6A g-1Discharge capacity is up to 820.0mAh g respectively after recycling 500 times under current density-1.The equipment that preparation method uses is simple, and process is easy to control, obtained negative electrode material high magnification capacity with higher and
Cyclical stability.
To achieve the above object, the invention provides the following technical scheme:
A kind of SnO2The preparation method of the porous compound lithium ion negative electrode material of-Fe-C, the specific steps of which are as follows:
(1) sn-containing compound, iron containing compounds, weak acid neutralizer, surfactant are dissolved in alcohol solution, are stirred
To mixed solution；
(2) step (1) solution is placed in reaction kettle in high temperature furnace and is heated；
(3) wash products after reacting, are then placed under reducing atmosphere and are heat-treated, obtain SnO2- Fe-C composite material.
In the step (1) sn-containing compound be di-n-octyltin oxide, phenyl tin trichloride, tin tetrachloride, tin fluoride,
At least one of stannous chloride, tributyltin chloride, trimethyltin chloride, stannous oxalate；Iron containing compounds are iron chloride, chlorine
Change ferrous iron, ferric phosphate, ammonium oxalate molysite, tri-iron dodecacarbonyl, ferrocene, ferric stearate, ironic citrate, two nonyl carbonyl irons, second
At least one of acyl acetone iron；Weak acid neutralizer be urea, sodium acetate, sodium carbonate, sodium bicarbonate, sodium citrate, ammonium acetate,
At least one of ammonium carbonate；Surfactant is alkylolamides, polyvinylpyrrolidone, lauryl sodium sulfate, 12
Alkyl benzene calcium sulfonate, sodium sulfate of polyethenoxy ether of fatty alcohol, cetyl trimethylammonium bromide, glycerin monostearate, three second
At least one of alkene tetramine；Alcohols is methanol, ethyl alcohol, ethylene glycol, glycerine, benzyl alcohol, cyclohexanol, 2- butanol, octanol, the last of the ten Heavenly stems
At least one of alcohol.
Preferably, sn-containing compound is at least one of tin tetrachloride, stannous oxalate；Iron containing compounds be iron chloride,
At least one of ammonium oxalate molysite；Weak acid neutralizer is at least one of urea, sodium citrate；Surfactant is poly- second
At least one of alkene pyrrolidone, cetyl trimethylammonium bromide；Alcohols is one of benzyl alcohol, ethylene glycol.
Optimal, sn-containing compound is tin tetrachloride；Iron containing compounds are ammonium oxalate iron；Weak acid neutralizer is citric acid
Sodium；Surfactant is polyvinylpyrrolidone；Alcohols is benzyl alcohol.
Sn-containing compound in the step (1), iron containing compounds, weak acid neutralizer molar ratio be 0.1~8:0.1~
8:0.2~32, preferred molar ratio are 0.4~4:0.4~4:0.8~16, and optimal molar ratio is 0.5:1:6.
Alcohols volume is 30~90ml in the step (1), and surfactant qualities are 0~50g, solution mixing speed
For 400~900rpm, mixing time is 1~6h.
Solution is placed in 100ml reaction kettle in the step (2), and temperature-rise period is with 3~10 DEG C of min-1Heating rate
It is reacted from room temperature to 160~220 DEG C and keeps the temperature 6~36h.
Cleaning uses ethyl alcohol eccentric cleaning in the step (3), and wash number is 2~4 times, and centrifugal speed is 5000~
12000rpm, centrifugation time are 3~20min；The mixed gas of heat treatment atmosphere hydrogen and nitrogen or argon gas, hydrogen and indifferent gas
Body volume ratio is 0~1:1~100, and heat treatment includes two stages: 1) temperature rise period: from room temperature to holding temperature, heating rate
For 0.2~15 DEG C/min；2) holding stage: in 350~650 DEG C of 3~12h of insulation reaction.
SnO is made in the present invention2The porous compound lithium ion negative electrode material of-Fe-C includes porous carbon matrix and is equably embedded in
The SnO of porous carbon content2With Fe nano particle, SnO2- Fe-C composite material has the patterns such as sheet, tufted, having a size of
500nm~100 μm, SnO2It is 1~600nm with Fe nanoparticle size.
The method that the material made from above-mentioned steps prepares lithium ion battery, key step are as follows: by SnO2- Fe-C is compound
Material, carbon black and Kynoar are uniformly mixed, and pulp object even spread is sufficiently stirred by solvent of N-Methyl pyrrolidone
Negative electrode film is formed on copper foil.
SnO in above-mentioned resulting lithium ion battery2- Fe-C composite material, carbon black and Kynoar (PVDF) mass ratio
For 8~20:0~1:1.
Compared with prior art, the beneficial effects of the present invention are:
(1) the present invention is based on solvent-thermal methods, synthesize Sn-Fe complex alkoxide by easy steps, then control heat by condition
The controllable porous SnO of micro-structure can be obtained by decomposing2- Fe-C composite material.
(2) present invention realizes Sn, Fe element in product the chelation of metal ion in the high temperature process by alcohols
Middle molecular level is other evenly dispersed, can get the structural homogeneity of remote super existing composite material by this method.In addition, by anti-
It answers the control of condition that can adjust the pattern and microstructure features of combination product easily, can realize SnO by the method2-Fe-C
The large-scale production and application of nano composite anode material.
(3) compared with conventional lithium ion battery negative electrode material, the present invention creatively uses Fe nano particle to SnO2's
Charge and discharge process carries out situ catalytic, significantly increases its high magnification capacity and cyclical stability.Meanwhile by SnO2, Fe nanometers
Grain is uniformly embedded in the porous carbon matrix of alkoxide decomposition generation, can further promote SnO2The electricity of-Fe-C nanocomposite
Chemical activity and structural stability.
Detailed description of the invention
Fig. 1 is SnO made from embodiment 12The Flied emission Electronic Speculum (FESEM) (A) and transmission electricity of the nano combined product of-Fe-C
Mirror (TEM) (B) photo；
Fig. 2 is SnO made from embodiment 12- Fe-C nanometer sheet is in 1A g-1Chemical property under current density condition；
Fig. 3 is SnO prepared by embodiment 22The FESEM photo of the nano combined product of-Fe-C；
Fig. 4 is SnO prepared by embodiment 32The FESEM photo of the nano combined product of-Fe-C；
Fig. 5 is the SnO in comparative example 12Nanoparticle agglomerates and the uneven situation of carbon coating layer；
Fig. 6 is the discharge capacity situation of comparative example 2.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of SnO2The preparation method of the porous compound lithium ion negative electrode material of-Fe-C, the specific steps of which are as follows:
(1) weigh 0.5mmol tin tetrachloride, 1mmol ammonium oxalate iron, 6mmol sodium citrate, 10g polyvinylpyrrolidone,
It is dissolved in 70ml benzyl alcohol, solution mixing speed is 800rpm, mixing time 2h；
(2) step (1) solution is placed in 100ml reaction kettle, temperature-rise period is with 6 DEG C of min-1Heating rate is from room temperature liter
Temperature reacts to 190 DEG C and keeps the temperature 12h；
(3) by step (2) product ethyl alcohol eccentric cleaning, wash number is 3 times, centrifugal speed 7000rpm, when centrifugation
Between be 10min；Then product is heat-treated in the mixed gas of hydrogen and nitrogen, hydrogen is with nitrogen gas volume ratio
1:99, heat treatment include two stages: 1) temperature rise period: from room temperature to holding temperature, heating rate is 6 DEG C/min；2) it keeps the temperature
Stage: it in 600 DEG C of insulation reaction 4h, finally naturally cools to room temperature and obtains SnO2The nano combined product of-Fe-C.
By 1 gained SnO of embodiment2The nano combined product of-Fe-C, carbon black and Kynoar (PVDF) in mass ratio 90:
0:10 mixing is to be uniformly coated on copper foil after pulp object is sufficiently stirred in dispersing agent with N-Methyl pyrrolidone (NMP), 120
DEG C vacuum drying 12h after be cut into 13mm diameter circular negative electrode tab.With lithium piece to be positive in the glove box full of argon gas,
Celgard 2400 is diaphragm, and electrolyte is 1mol/L (being converted into mol/L expression) LiPF6/ diethyl carbonate+ethylene carbonate
(volume ratio 1:1) is completed the CR2032 button cell that experiment uses.Using battery test system (BTS-5V50mA type,
New Weir) electrochemical property test is carried out at 25 DEG C, charge and discharge range is 0.01~3.0V.
From Figure 1A it can be found that SnO2The nano combined product morphology of-Fe-C is monodisperse micron chip, and width is 6 μm, thickness
About 30nm has flourishing cellular structure in nanometer sheet.The visible intensive SnO of Figure 1B2, Fe uniform particle in the carbon matrix,
And average grain diameter statistics is 20nm.
Fig. 2 it is visible its in 1A g-1Discharge capacity is up to 1041.3mAh g after recycling 200 times under current density-1.In addition,
Further test is shown in 6A g-1Its discharge capacity is up to 820.0mAh g after recycling 500 times under current density-1。
Embodiment 2
A kind of SnO2The preparation method of the porous compound lithium ion negative electrode material of-Fe-C, the specific steps of which are as follows:
(1) 2mmol tin fluoride, 1mmol ammonium oxalate molysite, 12mmol ammonium acetate, 20g fatty alcohol polyoxyethylene ether sulphur are weighed
Sour sodium is dissolved in 85ml cyclohexanol, and solution mixing speed is 600rpm, mixing time 1h；
(2) step (1) solution is placed in 100ml reaction kettle, temperature-rise period is with 3 DEG C of min-1Heating rate is from room temperature liter
Temperature is reacted to 200 DEG C and is kept the temperature for 24 hours；
(3) by step (2) product ethyl alcohol eccentric cleaning, wash number is 4 times, centrifugal speed 8000rpm, when centrifugation
Between be 5min；Then product is heat-treated in the mixed gas of hydrogen and nitrogen, hydrogen is with nitrogen gas volume ratio
1:60, heat treatment include two stages: 1) temperature rise period: from room temperature to holding temperature, heating rate is 4 DEG C/min；2) it keeps the temperature
Stage: it in 350 DEG C of insulation reaction 3h, finally naturally cools to room temperature and obtains SnO2The nano combined product of-Fe-C.
By 2 gained SnO of embodiment2The nano combined product of-Fe-C, carbon black and Kynoar (PVDF) in mass ratio 90:
5:5 mixing is to be uniformly coated on copper foil after pulp object is sufficiently stirred in dispersing agent with N-Methyl pyrrolidone (NMP), 110 DEG C
13mm diameter circular negative electrode tab is cut into vacuum drying afterwards for 24 hours.It is positive, celgard with lithium piece in the glove box full of argon gas
2400 be diaphragm, and electrolyte is 1mol/L (being converted into mol/L expression) LiPF6/ diethyl carbonate+ethylene carbonate (volume ratio
For 1:1), it is completed the CR2032 button cell that experiment uses.Using battery test system (BTS-5V50mA type, new Weir)
Electrochemical property test is carried out at room temperature, and charge and discharge range is 0.01~3.0V.
Embodiment 2 and embodiment 1 compare the visible pattern and micro-structure for leading to combination product by the regulation of reaction condition
It changes, as seen from Figure 3, for combination product by 6 μm of width of micron chip in embodiment 1, thickness about 30nm is changed into embodiment 2
In it is 12 μm wide, 18nm is thick, while a large amount of SnO2- Fe nano particle is transferred to carbon matrix surface, and partial size is up to about 400nm.It is led
Wanting performance is 1A g-1Discharge capacity is up to 849.3mAh g after recycling 200 times under current density-1, in 6A g-1Under current density
Discharge capacity is 648.3mAh g after circulation 500 times-1。
Embodiment 3
A kind of SnO2The preparation method of the porous compound lithium ion negative electrode material of-Fe-C, the specific steps of which are as follows:
(1) 2mmol tributyltin chloride, 1mmol ironic citrate, 12mmol urea, 20g cetyl trimethyl bromine are weighed
Change ammonium, be dissolved in 90ml glycerine, solution mixing speed is 900rpm, mixing time 5h；
(2) step (1) solution is placed in 100ml reaction kettle, temperature-rise period is with 1 DEG C of min-1Heating rate is from room temperature liter
Temperature reacts to 210 DEG C and keeps the temperature 36h；
(3) by step (2) product ethyl alcohol eccentric cleaning, wash number is 5 times, centrifugal speed 10000rpm, centrifugation
Time is 15min；Then product is heat-treated in the mixed gas of hydrogen and nitrogen, hydrogen and nitrogen gas volume ratio
For 1:50, heat treatment includes two stages: 1) temperature rise period: from room temperature to holding temperature, heating rate is 2 DEG C/min；2) it protects
Thermophase: it in 550 DEG C of insulation reaction 2.5h, finally naturally cools to room temperature and obtains SnO2The nano combined product of-Fe-C.
By 3 gained SnO of embodiment2The nano combined product of-Fe-C, carbon black and Kynoar (PVDF) in mass ratio 95:
0:5 mixing is to be uniformly coated on copper foil after pulp object is sufficiently stirred in dispersing agent with N-Methyl pyrrolidone (NMP), 100 DEG C
13mm diameter circular negative electrode tab is cut into after vacuum drying 12h.It is positive, celgard with lithium piece in the glove box full of argon gas
2400 be diaphragm, and electrolyte is 1mol/L (being converted into mol/L expression) LiPF6/ diethyl carbonate+ethylene carbonate (volume ratio
For 1:1), it is completed the CR2032 button cell that experiment uses.Using battery test system (BTS-5V50mA type, new Weir)
Electrochemical property test is carried out at room temperature, and charge and discharge range is 0.01~3.0V.
Embodiment 3 and example 1 compare the visible control by reaction condition can adjust easily the pattern of combination product with it is micro-
Structure feature, by adjusting raw material type and proportion, size about 4 in 2 for combination product is changed by the micron chip in embodiment 1
μm tufted structure (Fig. 4), and soilless sticking and adhesion phenomenon between cluster, this flourishing SnO2- Fe-C nanometers of branch are conducive to
Electronics conduction is transported with lithium ion.Its main performance is 1A g-1Discharge capacity is reachable after recycling 200 times under current density
983.5mAh g-1, in 6A g-1Discharge capacity is 725.3mAh g after recycling 500 times under current density-1。
For prominent beneficial effects of the present invention, following comparative example is enumerated.
Comparative example 1
Previous SnO2Base carbon composite often first prepares SnO2Nano particle, then carbon coating layer is introduced on surface.Example
Hydro-thermal method preparation SnO is first passed through as described in patent CN109437288A2Base composite nano particle, then be passed through at acetylene gas body heat
Reason carries out carbon-coating cladding.But caning be found that has apparent SnO by material prepared by similar approach2Nanoparticle agglomerates and carbon packet
Coating problem of non-uniform (Fig. 5).Compared with previous preparation method, the application is using alcohols in the high temperature process to metal ion
Chelating realizes that Sn, Fe element molecular level are other evenly dispersed, aoxidizes to obtain remote super existing composite material by decomposition in situ
Structural homogeneity.
Comparative example 2
Composite material obtained by traditional technology often faces the problem that charge/discharge capacity is low, cycle life is poor, such as patent
SnO described in CN201410202070.52Discharged capacity after/graphene composite lithium ion battery cathode material only recycles 30 times
It is reduced to about 350mAh g-1(Fig. 6).As it can be seen that the present invention is using Fe nano particle to SnO2Charge and discharge process carry out in situ urge
Change, obtains the rate capability and cyclical stability for being much higher than the prior art.
Comparative example 3
A kind of stannic oxide-graphene lithium cell cathode material, stannic oxide described in patent CN201811047789.0
Partial size is up to 50~100nm, it is remote it is super it is of the invention in active particle partial size, excessive active particle partial size is significant adverse to electrification
The progress of reaction is learned, and capacity is only 520mAh g after it is recycled 90 times under 0.1C current density condition-1, also it is far below this hair
Bright gained charge-discharge performance.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of catalytic type SnO2- Fe-C lithium ion battery negative material, it is characterised in that: including porous carbon matrix and equably
It is embedded in the SnO of porous carbon content2With Fe nano particle.
2. catalytic type SnO according to claim 12- Fe-C lithium ion battery negative material, it is characterised in that: its pattern packet
Include sheet or tufted；Having a size of 500nm~100 μm；SnO2It is 1~600nm with Fe nanoparticle size.
3. catalytic type SnO of any of claims 1 or 22The preparation method of-Fe-C lithium ion battery negative material, feature exist
In, comprising the following steps:
(1) sn-containing compound, iron containing compounds, weak acid neutralizer, surfactant are dissolved in alcohol solution, are stirred to get mixed
Close solution；
(2) step (1) solution is placed in reaction kettle in high temperature furnace and is heated；
(3) wash products after reacting, are then placed under reducing atmosphere and are heat-treated, obtain SnO2- Fe-C composite material.
4. catalytic type SnO according to claim 32The preparation method of-Fe-C lithium ion battery negative material, feature exist
In: sn-containing compound is di-n-octyltin oxide, phenyl tin trichloride, tin tetrachloride, tin fluoride, chlorination in the step (1)
At least one of stannous, tributyltin chloride, trimethyltin chloride, stannous oxalate；
The iron containing compounds are iron chloride, frerrous chloride, ferric phosphate, ammonium oxalate molysite, tri-iron dodecacarbonyl, ferrocene, hard
At least one of resin acid iron, ironic citrate, two nonyl carbonyl irons, ferric acetyl acetonade；
The weak acid neutralizer be urea, sodium acetate, sodium carbonate, sodium bicarbonate, sodium citrate, ammonium acetate, in ammonium carbonate extremely
Few one kind；
The surfactant is alkylolamides, polyvinylpyrrolidone, lauryl sodium sulfate, dodecyl benzene sulfonic acid
Calcium, sodium sulfate of polyethenoxy ether of fatty alcohol, cetyl trimethylammonium bromide, glycerin monostearate, in triethylene tetramine
It is at least one；
The alcohols be methanol, ethyl alcohol, ethylene glycol, glycerine, benzyl alcohol, cyclohexanol, 2- butanol, octanol, in decyl alcohol at least
It is a kind of.
5. catalytic type SnO according to claim 42The preparation method of-Fe-C lithium ion battery negative material, feature exist
In: the sn-containing compound is at least one of tin tetrachloride, stannous oxalate；The iron containing compounds are iron chloride, oxalic acid
At least one of ammonium molysite；The weak acid neutralizer is at least one of urea, sodium citrate；The surfactant is
At least one of polyvinylpyrrolidone, cetyl trimethylammonium bromide；The alcohols is benzyl alcohol, one in ethylene glycol
Kind.
6. catalytic type SnO according to claim 52The preparation method of-Fe-C lithium ion battery negative material, feature exist
In: the sn-containing compound is tin tetrachloride；The iron containing compounds are ammonium oxalate iron；The weak acid neutralizer is citric acid
Sodium；The surfactant is polyvinylpyrrolidone；The alcohols is benzyl alcohol.
7. catalytic type SnO according to claim 32The preparation method of-Fe-C lithium ion battery negative material, feature exist
In the molar ratio of: sn-containing compound in the step (1), iron containing compounds, weak acid neutralizer be 0.1~8:0.1~8:0.2
~32；
Alcohols volume is 30~90ml in the step (1), and surfactant qualities are 0~50g, and solution mixing speed is
400~900rpm, mixing time are 1~6h；
Solution is placed in 100ml reaction kettle in the step (2), and temperature-rise period is with 3~10 DEG C of min-1Heating rate is from room
Temperature is warming up to 160~220 DEG C and reacts and keep the temperature 6~36h；
Cleaning uses ethyl alcohol eccentric cleaning in the step (3), and wash number is 2~4 times, and centrifugal speed is 5000~
12000rpm, centrifugation time are 3~20min；The mixed gas of heat treatment atmosphere hydrogen and nitrogen or argon gas, hydrogen and indifferent gas
Body volume ratio is 0~1:1~100, and heat treatment includes two stages: 1) temperature rise period: from room temperature to holding temperature, heating rate
For 0.2~15 DEG C/min；2) holding stage: in 350~650 DEG C of 3~12h of insulation reaction.
8. catalytic type SnO according to claim 72The preparation method of-Fe-C lithium ion battery negative material, feature exist
In the molar ratio of: sn-containing compound in the step (1), iron containing compounds, weak acid neutralizer be 0.4~4:0.4~4:0.8
~16.
9. catalytic type SnO according to claim 82The preparation method of-Fe-C lithium ion battery negative material, feature exist
In the molar ratio of: sn-containing compound in the step (1), iron containing compounds, weak acid neutralizer be 0.5:1:6.
10. catalytic type SnO of any of claims 1 or 22- Fe-C lithium ion battery negative material is in preparing lithium ion battery
Using, it is characterised in that: by SnO2- Fe-C composite material, carbon black and Kynoar are uniformly mixed, with N-Methyl pyrrolidone
It pulp object is sufficiently stirred for solvent is uniformly coated on copper foil and form negative electrode film；SnO in resulting lithium ion battery2-Fe-C
Composite material, carbon black and Kynoar mass ratio are 8~20:0~1:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931767A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof |
| CN111908500A (en) * | 2020-07-20 | 2020-11-10 | 西安工程大学 | Preparation method of silver-doped tin dioxide nanosheet self-assembled flower-shaped material |
| CN112978704A (en) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | Modified lithium iron phosphate material and preparation method thereof |
| CN114927676A (en) * | 2022-05-06 | 2022-08-19 | 益阳生力材料科技股份有限公司 | Three-dimensional cluster antimony material and preparation method and application thereof |
-
2019
- 2019-08-05 CN CN201910717143.7A patent/CN110429259A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931767A (en) * | 2019-12-19 | 2020-03-27 | 温州涂屋信息科技有限公司 | SnO modified by carbon-coated FeCo alloy2Negative electrode material of sodium ion battery and preparation method thereof |
| CN111908500A (en) * | 2020-07-20 | 2020-11-10 | 西安工程大学 | Preparation method of silver-doped tin dioxide nanosheet self-assembled flower-shaped material |
| CN112978704A (en) * | 2021-05-08 | 2021-06-18 | 蜂巢能源科技有限公司 | Modified lithium iron phosphate material and preparation method thereof |
| CN112978704B (en) * | 2021-05-08 | 2021-10-15 | 蜂巢能源科技有限公司 | Modified lithium iron phosphate material and preparation method thereof |
| CN114927676A (en) * | 2022-05-06 | 2022-08-19 | 益阳生力材料科技股份有限公司 | Three-dimensional cluster antimony material and preparation method and application thereof |
| CN114927676B (en) * | 2022-05-06 | 2023-08-29 | 益阳生力材料科技股份有限公司 | Three-dimensional clustered antimony material and preparation method and application thereof |
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