CN109449379A - A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof - Google Patents

A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof Download PDF

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CN109449379A
CN109449379A CN201811059753.4A CN201811059753A CN109449379A CN 109449379 A CN109449379 A CN 109449379A CN 201811059753 A CN201811059753 A CN 201811059753A CN 109449379 A CN109449379 A CN 109449379A
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CN109449379B (en
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关冬彩
孙艳辉
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South China Normal University
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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
    • 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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses a kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof, the lithium ion battery negative material the preparation method is as follows: 1) source of iron and tin source be co-precipitated under the action of surface active agent tween -20 generate SnFe2O4Nano particle；2)SnFe2O4Nano particle and Dopamine hydrochloride react in Tris-HCl buffer, prepare presoma；3) calcining of presoma under an inert atmosphere.Lithium ion battery negative material of the invention is a kind of SnFe that nitrogen-doped carbon is compound2O4Nano particle has many advantages, such as that stable structure, efficiency for charge-discharge are high, cycle performance is excellent, electrochemical reversibility is good, and preparation process is simple, at low cost, environmental-friendly, is suitble to lithium ion battery practical application, can be realized industrialization large-scale production.

Description

A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and its preparation side Method and application
Technical field
The present invention relates to a kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and preparation method thereof with answer With belonging to technical field of lithium ion.
Background technique
Currently, theoretical capacity (the 372mAhg of commercialized graphite cathode material-1) lower, lithium ion diffusion rate compared with It is small, it can no longer meet the development trend of lithium ion battery high-energy density, high power charging-discharging ability.Therefore, searching can be replaced Become a big hot spot in Study on Li-ion batteries field in recent years for the novel anode material of graphite.
In numerous negative electrode materials, Sn base negative electrode material theoretical specific capacity with higher, such as SnO2(1494mAh·g-1)、SnO(1138mAh·g-1)、Sn(991mAh·g-1), and lower production costs, it is considered most application prospect.However, tin There are two big defects for base negative electrode material: 1) SnOxAnd Li+Conversion reaction it is irreversible, cause the loss of first circle charge/discharge capacity serious, Coulombic efficiency only 50% or so；2) metal Sn and Li+Alloy/that removal alloying reaction can make metal Sn generate huge volume is swollen Swollen (up to 300%), Sn sill is caused to deform, crack and fall off, electrical contact performance is deteriorated, and ultimately causes material Specific capacity declines rapidly.
To solve the above-mentioned problems, recent domestic researcher by by material nano or special construction to reduce The absolute volume expansion of embedding lithium/de- lithium process, or by adulterating or coating other substances to effectively slow using synergistic effect The volume expansion generated in solution charge and discharge process.Such as: prepare the binary metal oxide transition metal with spinel structure Hydrochlorate AFe2O4(A Zn, Co, Ni, Cu or Mn), by improving Li+Deintercalation and holding charge and discharge process in spinel structure Stable structure excessively expand improving the volume of single metal oxide and stability problem.
Ferrous acid tin (SnFe2O4) be a kind of inverse spinel structure material, it is logical with three-dimensional diffusion in inverse spinel structure Road is conducive to Li+Diffusion mobility, be also beneficial to high power charging-discharging, charge and discharge platform (about 1.05V) is lower than other mistakes Cross metal oxide, theoretical specific capacity (about 1130mAhg-1) it is higher than simple metal oxide and inactive ferrite (such as CuFe2O4).However, ferrous acid tin electric conductivity in lithium ion battery charge and discharge process is low, cubical expansivity is excessive, will cause Material structure destroys, and then the performances dramatic decrease such as lead to specific capacity, cyclical stability.Therefore, by improve material structure or The carbon material for adulterating good conductivity prepares a kind of cheap, environmental-friendly SnFe2O4The lithium-ion electric negative electrode material compound with carbon, Specific capacity, coulombic efficiency, high rate performance and cyclical stability that lithium battery discharges for the first time are improved, is had to field of lithium ion battery Significance.
Summary of the invention
The purpose of the present invention is to provide a kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and its system Preparation Method and application.
The technical solution used in the present invention is:
A kind of SnFe that nitrogen-doped carbon is compound2O4The preparation method of lithium ion battery negative material, comprising the following steps:
1) source of iron and tin source are added in Tween-20 aqueous solution simultaneously, mixing is sufficiently stirred, adds aqueous slkali, fills Divide reaction, separation and collection sediment, obtains SnFe2O4Nano particle；
2) by SnFe2O4Nano particle and Dopamine hydrochloride are added in Tris-HCl buffer, sufficiently react, then be centrifuged receipts Collect solid product, obtains presoma；
3) presoma is placed under inert atmosphere, is calcined, obtain the compound SnFe of nitrogen-doped carbon2O4Lithium ion battery Negative electrode material.
The molar ratio of Fe, Sn are 1:0.5 in step 1).
Step 1) the source of iron is Iron dichloride tetrahydrate, ferric trichloride, Fe(NO3)39H2O, ferrous oxalate, sulfuric acid Asia At least one of iron, ferric sulfate.
Step 1) the tin source is at least one of two hydrated stannous chlorides, stannous sulfate.
Step 1) the Tween-20 aqueous solution is by Tween-20 and water according to volume ratio 1:(10~50) it mixes.
Step 1) the aqueous slkali is one of NaOH solution, ammonium hydroxide.
Step 1) the reaction carries out at 20~80 DEG C, and the reaction time is 2~4h.
Step 2) the SnFe2O4Nano particle, Dopamine hydrochloride mass ratio be 1:(0.1~0.5).
Step 2) the reaction carries out at 20~80 DEG C, and the reaction time is 2~4h.
Step 3) the calcining specifically: be warming up to 600~800 DEG C with the rate of 1~5 DEG C/min and keep 1~2h.
The beneficial effects of the present invention are: lithium ion battery negative material of the invention is that a kind of nitrogen-doped carbon is compound SnFe2O4Nano particle (SnFe2O4@NC), with stable structure, efficiency for charge-discharge is high, cycle performance is excellent, electrochemical reversible Property it is good the advantages that, preparation process is simple, at low cost, environmental-friendly, be suitble to lithium ion battery practical application, can be realized work Industryization large-scale production.
1) SnFe in the present invention2O4Storage lithium mechanism be related to Li+Deintercalation, Li in inverse spinel three-dimensional channel+With SnO And Fe2O3Conversion reaction, Li+With three kinds of alloying reaction of metal Sn, charge and discharge platform it is low he in its transiting metal oxidation Object, theoretical specific capacity 1130mAhg-1, it is higher than SnO, Fe2O3Etc. single metal oxides；
2) N doping carbon-coating in the present invention has good electric conductivity, and SnFe can be improved2O4The conductivity of@NC, thus Preferable high rate performance is shown in charge and discharge process；
3) N doping carbon-coating in the present invention can be used as buffer layer, and the body of material in charge and discharge process can be effectively relieved Product variation, ensure that the stable structure of material, to improve the cycle performance and high rate performance of material；
4) SnFe in the present invention2O4The synthetic method of nano particle and its very simple with the polymerization of Dopamine hydrochloride, Low production cost, energy consumption are lower, environmental-friendly, are suitble to lithium ion battery practical application, and it is extensive raw to can be realized industrialization It produces.
Detailed description of the invention
Fig. 1 is the SnFe of embodiment 12O4With the SnFe of Examples 1 to 32O4The X-ray powder diffraction figure (XRD) of@NC.
Fig. 2 is the SnFe of embodiment 12O4The scanning electron microscope (SEM) photograph (SEM) of@NC.
Fig. 3 is the SnFe of embodiment 12O4The CV curve graph of preceding 3 circle of the half-cell circulation of@NC assembling.
Fig. 4 is the SnFe of embodiment 12O4The half-cell of assembling is in current density 0.2Ag-1Under cycle performance figure.
Fig. 5 is the SnFe of embodiment 12O4The half-cell of@NC assembling is in current density 0.2Ag-1Under cycle performance figure.
Fig. 6 is the SnFe of embodiment 12O4The high rate performance figure of the half-cell of@NC assembling.
Specific embodiment
A kind of SnFe that nitrogen-doped carbon is compound2O4The preparation method of lithium ion battery negative material, comprising the following steps:
1) source of iron and tin source are added in Tween-20 aqueous solution simultaneously, mixing is sufficiently stirred, adds aqueous slkali, fills Divide reaction, separation and collection sediment, obtains SnFe2O4Nano particle；
2) by SnFe2O4Nano particle and Dopamine hydrochloride are added in Tris-HCl buffer, sufficiently react, then be centrifuged receipts Collect solid product, obtains presoma；
3) presoma is placed under inert atmosphere, is calcined, obtain the compound SnFe of nitrogen-doped carbon2O4Lithium ion battery Negative electrode material (SnFe2O4@NC)。
Preferably, the molar ratio of Fe, Sn are 1:0.5 in step 1).
Preferably, concentration of the step 1) source of iron in Tween-20 aqueous solution is 0.02~0.5mol/L.
Preferably, concentration of the step 1) tin source in Tween-20 aqueous solution is 0.01~0.1mol/L.
Preferably, the step 1) source of iron be Iron dichloride tetrahydrate, ferric trichloride, Fe(NO3)39H2O, ferrous oxalate, At least one of ferrous sulfate, ferric sulfate.
It is further preferred that the step 1) source of iron is at least one of Iron dichloride tetrahydrate, Fe(NO3)39H2O.
Preferably, the step 1) tin source is at least one of two hydrated stannous chlorides, stannous sulfate.
Preferably, step 1) the Tween-20 aqueous solution is by Tween-20 and water according to volume ratio 1:(10~50) mixing and At.
Preferably, the step 1) aqueous slkali is one of NaOH solution, ammonium hydroxide, for adjusting the pH value of reaction solution To more than 10.
Preferably, the step 1) reaction carries out at 20~80 DEG C, and the reaction time is 2~4h.
Preferably, the step 2) SnFe2O4Nano particle, Dopamine hydrochloride mass ratio be 1:(0.1~0.5).
Preferably, the step 2) reaction carries out at 20~80 DEG C, and the reaction time is 2~4h.
Preferably, the step 3) inert atmosphere is nitrogen atmosphere or argon atmosphere.
Preferably, the step 3) calcining specifically: be warming up to 600~800 DEG C with the rate of 1~5 DEG C/min and keep 1 ~2h.
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material (SnFe2O4@NC) preparation method, including Following steps:
1) by the FeCl of 12mmol2·4H2The SnCl of O and 6mmol2·2H2O is added to the Tween-20 water of 150mL simultaneously In solution (being formulated by Tween-20 and distilled water according to volume ratio 1:10), mixing is sufficiently stirred, adding concentration is 3h, separation and collection sediment are stirred at the NaOH solution of 4mol/L to pH value > 10,80 DEG C of reaction solution, are washed with distilled water Sediment is multiple, and dry 10h, obtains SnFe at 60 DEG C2O4Nano particle (XRD diagram is as shown in Figure 1)；
2) SnFe for being 1:0.3 by mass ratio2O4It is 10mmol/L's that nano particle and Dopamine hydrochloride, which are added to concentration, In Tris-HCl buffer (pH=8.5), 4h is stirred at 80 DEG C, then solid product is collected by centrifugation, be washed with distilled water solid production Object is multiple, and dry 10h, obtains presoma at 60 DEG C；
3) presoma is placed under nitrogen atmosphere, is raised to 700 DEG C with the rate of 5 DEG C/min and keeps 1h, obtain N doping The compound SnFe of carbon2O4(XRD diagram is as shown in Figure 1 for lithium ion battery negative material；SEM figure is as shown in Figure 2).
Respectively with SnFe2O4Nano particle and SnFe2O4@NC is negative electrode active material, is assembled into lithium ion knob with lithium metal Half-cell is detained, electrochemical property test is carried out.
The assembly of lithium ion button half-cell: by negative electrode active material, Super P Li conductive black and gather inclined difluoro second Alkene 8:1:1 in mass ratio mixing, is mixed well with N-Methyl pyrrolidone, stirs into thick, be coated on copper foil, vacuum 120 DEG C dry 10h, is cut into the pole piece of diameter about 12mm as working electrode, Li piece is to electrode.Diaphragm is that Celgard polyethylene is micro- Pore membrane, electrolyte are the LiPF of concentration 1mol/L6Ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) mixed electrolytic solution (volume ratio of EC, DMC, EMC are 1:1:1 in mixed electrolytic solution).
Half-cell is assembled using CR2032 type button cell in the glove box of applying argon gas.
Electrochemical property test: it uses Neware CT-3008 type battery test system (the new Weir Electronics Co., Ltd. in Shenzhen) It is tested.
The SnFe of embodiment 12O4The CV curve graph of preceding 3 circle of the half-cell circulation of@NC assembling it is as shown in Figure 3 (test condition: 0.01~3.0V sweeps fast 0.1mV/s).
The SnFe of embodiment 12O4The half-cell of assembling is in current density 0.2Ag-1Under cycle performance figure such as Fig. 4 institute Show.
The SnFe of embodiment 12O4The half-cell of@NC assembling is in current density 0.2Ag-1Under cycle performance figure such as Fig. 5 It is shown.
The SnFe of embodiment 12O4The high rate performance figure of the half-cell of@NC assembling is as shown in Figure 6.
Embodiment 2:
A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material (SnFe2O4@NC) preparation method, including Following steps:
1) by the Fe (NO of 15mmol3)3·9H2The SnCl of O and 7.5mmol2·2H2O is added to the tween-of 150mL simultaneously In 20 aqueous solutions (being formulated by Tween-20 and distilled water according to volume ratio 1:25), mixing is sufficiently stirred, adding concentration is 4h, separation and collection sediment are stirred at the NaOH solution of 4mol/L to pH value > 10,25 DEG C of reaction solution, are washed with distilled water Sediment is multiple, and dry 6h, obtains SnFe at 80 DEG C2O4Nano particle；
2) SnFe for being 1:0.1 by mass ratio2O4It is 10mmol/L's that nano particle and Dopamine hydrochloride, which are added to concentration, In Tris-HCl buffer (pH=8.5), 6h is stirred at 25 DEG C, then solid product is collected by centrifugation, be washed with distilled water solid production Object is multiple, and dry 10h, obtains presoma at 80 DEG C；
3) presoma is placed under argon atmosphere, is raised to 600 DEG C with the rate of 2 DEG C/min and keeps 2h, obtain N doping The compound SnFe of carbon2O4(XRD diagram is as shown in Figure 1 for lithium ion battery negative material；Product pattern is consistent with embodiment 1).
Embodiment 3:
A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material (SnFe2O4@NC) preparation method, including Following steps:
1) by the Fe (NO of 15mmol3)3·9H2The SnCl of O and 7.5mmol2·2H2O is added to the tween-of 150mL simultaneously In 20 aqueous solutions (being formulated by Tween-20 and distilled water according to volume ratio 1:10), mixing is sufficiently stirred, adds quality point 2h, separation and collection sediment are stirred at the ammonium hydroxide of number 25% to pH value > 10,80 DEG C of reaction solution, are washed with distilled water precipitating Object is multiple, and dry 10h, obtains SnFe at 60 DEG C2O4Nano particle；
2) SnFe for being 1:0.5 by mass ratio2O4It is 10mmol/L's that nano particle and Dopamine hydrochloride, which are added to concentration, In Tris-HCl buffer (pH=8.5), 4h is stirred at 50 DEG C, then solid product is collected by centrifugation, be washed with distilled water solid production Object is multiple, and dry 10h, obtains presoma at 60 DEG C；
3) presoma is placed under nitrogen atmosphere, is raised to 700 DEG C with the rate of 5 DEG C/min and keeps 1h, obtain N doping The compound SnFe of carbon2O4(XRD diagram is as shown in Figure 1 for lithium ion battery negative material；Product pattern is consistent with embodiment 1).
Test result analysis:
As shown in Figure 1: the SnFe of embodiment 12O4With the SnFe of Examples 1 to 32O4The crystal diffraction peak of@NC is and standard JCPDS#11-0614SnFe2O4Crystal diffraction peak correspond.
As shown in Figure 2: SnFe prepared by embodiment 12O4@NC is in granular form, and grain diameter is 50~100nm.
As shown in Figure 3: there are apparent redox peaks in first lap in figure, wherein electric discharge branch respectively corresponds Li+Insertion Inverse spinel structure (1.3~1.5V weak peak), Li+With Sn2+And Fe3+Redox reaction, with SEI film generation (0.5V), Sn and Li+Alloying reaction (0.05V)；Charging branch respectively corresponds LixSn removal alloying reacts (0.15V), Sn With Fe and Li2The redox reaction (1.65V) of O.Two or three circles are in addition to Li later+With Sn2+And Fe3+Redox reaction move to right Outside to 0.77V, other peak positions are essentially coincided with first lap, show that the invertibity of reaction is good.
As shown in Figure 4: the SnFe of embodiment 12O4With good cycle performance and self-propagation performance.
As shown in Figure 5: the SnFe of embodiment 12O4@NC has good stable circulation performance.
As shown in Figure 6: the SnFe of embodiment 12O4@NC has good high rate performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of SnFe that nitrogen-doped carbon is compound2O4The preparation method of lithium ion battery negative material, it is characterised in that: including with Lower step:
1) source of iron and tin source are added in Tween-20 aqueous solution simultaneously, mixing is sufficiently stirred, adds aqueous slkali, it is sufficiently anti- It answers, separates and collect sediment, obtain SnFe2O4Nano particle；
2) by SnFe2O4Nano particle and Dopamine hydrochloride are added in Tris-HCl buffer, sufficiently react, then are collected by centrifugation solid Body product, obtains presoma；
3) presoma is placed under inert atmosphere, is calcined, obtain the compound SnFe of nitrogen-doped carbon2O4Negative electrode of lithium ion battery Material.
2. preparation method according to claim 1, it is characterised in that: the molar ratio of Fe, Sn are 1:0.5 in step 1).
3. preparation method according to claim 1 or 2, it is characterised in that: the step 1) source of iron is that four chloride hydrates are sub- At least one of iron, ferric trichloride, Fe(NO3)39H2O, ferrous oxalate, ferrous sulfate, ferric sulfate；Step 1) the tin source For at least one of two hydrated stannous chlorides, stannous sulfate.
4. preparation method according to claim 1, it is characterised in that: step 1) the Tween-20 aqueous solution is by Tween-20 With water according to volume ratio 1:(10~50) it mixes；Step 1) the aqueous slkali is one of NaOH solution, ammonium hydroxide.
5. preparation method according to claim 1 or 4, it is characterised in that: step 1) it is described reaction at 20~80 DEG C into Row, reaction time are 2~4h.
6. preparation method according to claim 1, it is characterised in that: the step 2) SnFe2O4Nano particle, hydrochloric acid are more The mass ratio of bar amine is 1:(0.1~0.5).
7. preparation method according to claim 1 or 6, it is characterised in that: step 2) it is described reaction at 20~80 DEG C into Row, reaction time are 2~4h.
8. preparation method according to claim 1, it is characterised in that: the step 3) calcining specifically: with 1~5 DEG C/ The rate of min is warming up to 600~800 DEG C and keeps 1~2h.
9. a kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material, it is characterised in that: by claim 1~8 Any one of described in method be prepared.
10. the compound SnFe of nitrogen-doped carbon as claimed in claim 92O4Lithium ion battery negative material is preparing lithium ion battery In application.
CN201811059753.4A 2018-09-12 2018-09-12 Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof Active CN109449379B (en)

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