CN105702945A - Liquid phase in-situ reduction-cold quenching preparation method of composite anode material and application of composite anode material - Google Patents
Liquid phase in-situ reduction-cold quenching preparation method of composite anode material and application of composite anode material Download PDFInfo
- Publication number
- CN105702945A CN105702945A CN201610118636.5A CN201610118636A CN105702945A CN 105702945 A CN105702945 A CN 105702945A CN 201610118636 A CN201610118636 A CN 201610118636A CN 105702945 A CN105702945 A CN 105702945A
- Authority
- CN
- China
- Prior art keywords
- negative pole
- composite negative
- snsbco
- preparation
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 liquid phase in-situ reduction-cold quenching preparation method of a composite anode material. With graphite as a raw material, graphite oxide is prepared by a modified Hummers method; the graphite oxide is ultrasonically dispersed into a solution of tin ions, antimony ions and cobalt ions; through an in-situ synthesis process, an SnSbCo alloy is generated in situ when the graphite oxide is reduced into graphene through a reducing agent by a titration-reduction method; liquid nitrogen is added for cold quenching treatment; and nano-alloy particles are firmly coated with the graphene and burnt at a certain temperature under an argon protection condition to prepare the SnSbCo/graphene composite anode material. Compared with the prior art, the preparation method disclosed by the invention effectively improves the material preparation efficiency and the structure stability; and a sodium-ion battery obtained by assembling the material has high charge-discharge specific capacity, good rate capability and cycle performance.
Description
Technical field
The present invention relates to technical field of new energies, particularly relate to liquid phase in-situ reducing-cold quenching preparation method and the application thereof of composite negative pole material。
Background technology
At present, the energy storage and conversion become restriction World Economics sustainable development major issue。High voltage, high-energy-density, self discharge be little and the advantage such as have extended cycle life owing to it possesses for lithium ion battery, obtains tremendous development in portable electrical power applications。The character of the sodium ion and lithium ion that are all I main group has many similarities, although sodium-ion battery progress is slow, but the progressively development along with accumulation power supply and electric automobile, the lithium resource in the whole world will be unable to effectively meet the great demand of power lithium-ion battery, thus will raise further and the price of lithium associated materials, increase battery cost, the final development hindering New Energy Industry。On the contrary, sodium-ion battery because of its raw material rich reserves (than lithium high 4～5 orders of magnitude), low price, the features such as environment green is friendly are increasingly becoming study hotspot, is widely regarded as the ideal chose of energy storage of future generation and electrokinetic cell。
Research finds, tri-kinds of metals of Pb, Sn, Sb with sodium ion, metallic alloying reaction can occur。Owing to Pb belongs to heavy metal material, contaminative is not widely studied greatly, and Na15Sn4、Na3Sb alloy can provide the theoretical specific capacity up to 847mAh/g, 660mAh/g respectively, is the anode material of lithium-ion battery of potential high power capacity。The research worker such as Xiao report sodium-ion battery SnSb/C negative material, under the electric current density of 55mA/g, charge and discharge cycles is after 125 weeks, specific capacity is stable reaches 97% (L.Xiao at 525mAh/g and coulombic efficiency, Y.Cao, J.Xiao, etal.ChemicalCommunications, 2012,48:3321-3323)。The specific capacity that metal Sn electrode circulates in the first two is up to 460mAh/g, but to the 3rd circulation, specific capacity can decay to 163mAh/g。Metal Sb electrode occurs in that quick special capacity fade equally, and after 20 circulations, capacity decays to below 100mAh/g from 342mAh/g rapidly。Na is all had the recyclability of extreme difference by visible two kinds of electrodes。Sn/C electrode is after 13 circulate, and specific capacity falls below the 20% of initial capacity, and Sb/C electrode is all very stable in front 30 circulations, reversible specific capacity is reduced to 397mAh/g from 494mAh/g, capability retention reaches 80.4%, but after circulating at 50, capacity decays to rapidly 100mAh/g。The research worker such as Lin adopt surfactant auxiliary wet chemistry method to be prepared for sodium-ion battery Sn0.9Cu0.1Negative material, under the electric current density of 169mA/g, charge and discharge cycles is after 100 weeks, capacity is stable at 420mAh/g, and capability retention is 97%, shows high cyclical stability, and pure Sn negative material is when identical discharge and recharge, the capacity of nanoscale Sn and micron order Sn only remains 250mAh/g and 66mAh/g (Y.M.Lin, PaulR.Abel, A.Gupta respectively, etal.ACSAppl.Mater.Interfaces, 2013,5,8273-8277)。
In order to solve this problem, the research worker such as Yui propose mixes Co, the chemical property that can make SnCo bianry alloy is superior to simple substance Sn, same circulation 30 weeks, and the capacity of SnCo is maintained at about 300mAh/g, and the basic loss of activity of simple substance Sn negative material (Y.Yui, Y.Ono, M.Hayashi, etal.JournaloftheElectrochemicalSociety, 2015,162:A3098-A3102)。But, the chemical property of this bianry alloy still can not meet existing requirement。
Graphene is widely used in the study on the modification of electrode material because possessing the feature of the mechanical strength that surface area is big, conductivity is superior and good。The Graphene obtained by chemistry redox has height defect, improve its conductivity on the contrary, modified Hummers method is such as adopted to prepare graphite oxide (GO), recycling electronation is removed oxygen-containing functional group and is obtained redox graphene (rGO), because it possesses high conductivity (16000Sm-1) and get most of the attention equally。Similar with Graphene, rGO show high resiliency, high conductivity and start to be applied to gradually sodium-ion battery as base material。Nithya passes through circulation 50 weeks under the chemical preparation electric current density of Sb/rGO, 131mA/g, and capacity maintains 598mAh/g, rGO, as substrate, makes material structure more firm (C.Nithya, S.Gopukumar.J.Mater.Chem.A., 2014,2:10516-10525)。Thus, it is necessary to sodium-ion battery is carried out the further research of composite negative pole material, to improve the charging and discharging capacity of electrode material and to improve its cycle performance。
Summary of the invention
The present invention solves the deficiencies in the prior art, there is provided a kind of with Graphene (rGO) for base material, bianry alloy SnSb basis introduces the third Elements C o, prepares the SnSbCo/ graphene composite negative pole with high charge-discharge specific capacity, good high rate performance。
It is an object of the invention to be realized by techniques below side:
Liquid phase in-situ reducing-cold quenching the preparation method of composite negative pole material, comprises the following steps:
(1) by pink salt, antimonic salt and salt solubility in solvent, mixing salt solution is obtained；By graphite oxide ultrasonic disperse in mixing salt solution；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise in the mixing salt solution of step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, by turbid solution in 50-80 DEG C of stirring reaction；
(3) after adding the quick cold quenching of liquid nitrogen in the turbid solution of step (2), vacuum filtration, repeatedly washing postlyophilization or vacuum drying, obtain SnSbCo/ Graphene precursor powder；
(4) under inert gas shielding, calcining at constant temperature at precursor powder is warming up to 200-450 DEG C with certain heating rate, obtain SnSbCo/ graphene composite negative pole。
Relative to prior art, the present invention passes through fabricated in situ technique, adopts titration reducing process to concurrently form a nanometer SnSbCo multi-nary alloy particles what prepare Graphene, is effectively improved material preparation efficiency；Add liquid nitrogen to cool down rapidly, make flake graphite alkene firmly wrap up SnSbCo alloying pellet by cold quenching technique, be effectively improved the structural stability of electrode material。
Further, in step (1) described mixing salt solution, the concentration of pink salt is 0.01-0.5mol/L, and the concentration of antimonic salt is 0.01-0.5mol/L, and the concentration of cobalt salt is 0.001-0.05mol/L；Tin ion, antimony ion, cobalt ion mol ratio be 1:1:0.1。
Further, the volume adding liquid nitrogen in step (3) is 0.5:1-2:1 with the volume ratio of turbid solution in step (2)。
Further, in the mixing salt solution that step (1) obtains, the concentration of graphite oxide is 0.5-2mg/mL。
Further, in step (2), the concentration of reducing solution is 0.1-2mol/L；Described reducing agent is hydrazine hydrate, ammonia, NaBH4With the one in HI。
Further, in step (1), ultrasonic power is 100-200W；Rate of addition in step (2) is 1-3mL/min；Mixing speed in step (2) is 200-1000r/min。
Further, described pink salt is stannous chloride or stannous acetate, and described antimonic salt is antimony chloride or antimony acetate, and described cobalt salt is cobaltous chloride or cobaltous acetate；Solvent described in step (1) and step (2) is the solvent of any one or the two mixing in deionized water, ethanol。
The preparation method that present invention also offers a kind of sodium-ion battery, comprise the following steps: by SnSbCo/ graphene composite negative pole, conductive black, binding agent according to mass ratio for (50-80): (30-10): be coated on Copper Foil after (20-10) mix homogeneously, vacuum drying, cut into slices after roll-in, obtain circular electric pole piece；Electrode slice, metallic sodium sheet, electrolyte are assembled into sodium-ion battery。Described SnSbCo/ graphene composite negative pole is the SnSbCo/ graphene composite negative pole that the above-mentioned any means mentioned prepares。
Relative to prior art, adopt the material of the present invention to assemble the sodium-ion battery obtained and there is high charge-discharge specific capacity, good high rate performance and cycle performance。
Further, described binding agent is the one in LA132, polyvinylidene fluoride or CMC binding agent；Described coating thickness is 60-120 μm；The thickness of described roll-in is 35-90 μm。
Present invention also offers a kind of sodium-ion battery, including circular electric pole piece, metallic sodium sheet and electrolyte, described circular electric pole piece is (50-80) by SnSbCo/ graphene composite negative pole, conductive black, binding agent according to mass ratio: (30-10): be coated on Copper Foil after (20-10) mix homogeneously, vacuum drying, after roll-in, section obtains, and described SnSbCo/ graphene composite negative pole is the SnSbCo/ graphene composite negative pole that the above-mentioned any means mentioned prepares。
Relative to prior art, the sodium-ion battery of the present invention adopts the SnSbCo/ graphene composite negative pole of the present invention so that sodium-ion battery has high charge-discharge specific capacity, good high rate performance and cycle performance。
In order to be more fully understood that and implement, describe the present invention in detail below in conjunction with accompanying drawing。
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the SnSbCo/ graphene composite negative pole that embodiment 1 prepares。
Fig. 2 is the SEM figure of the SnSbCo/ graphene composite negative pole that embodiment 1 prepares。
Fig. 3 is the TEM figure of the SnSbCo/ graphene composite negative pole that embodiment 1 prepares。
Fig. 4 is the XRD figure spectrum of the SnSbCo/ graphene composite negative pole that comparative example prepares。
Fig. 5 is the SEM figure of the SnSbCo/ graphene composite negative pole that comparative example prepares。
Fig. 6 is the TEM figure of the SnSbCo/ graphene composite negative pole that comparative example prepares。
Fig. 7 is the constant current charge-discharge performance map of the sodium-ion battery that the SnSbCo/ graphene composite negative pole that embodiment 1 prepares assembles。
Fig. 8 is the constant current charge-discharge performance map of the sodium-ion battery that the SnSbCo/ graphene composite negative pole that comparative example prepares assembles。
Detailed description of the invention
Liquid phase in-situ reducing-cold quenching the preparation method of composite negative pole material disclosed by the invention, comprises the following steps:
(1) by pink salt, antimonic salt and salt solubility in solvent, mixing salt solution is obtained；By graphite oxide ultrasonic disperse in mixing salt solution；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise in the mixing salt solution of step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, by turbid solution in 50-80 DEG C of stirring reaction 1-12h；
(3), after adding the quick cold quenching of liquid nitrogen in the turbid solution of step (2), carry out vacuum drying or lyophilization after vacuum filtration, repeatedly washing, obtain SnSbCo/ Graphene precursor powder；
(4) under inert gas shielding, calcining at constant temperature 2-6h at precursor powder is warming up to 200-450 DEG C with certain heating rate, obtain SnSbCo/ graphene composite negative pole。
Wherein, in the mixing salt solution of step (1), the concentration of pink salt is 0.01-0.5mol/L, and the concentration of antimonic salt is 0.01-0.5mol/L, and the concentration of cobalt salt is 0.001-0.05mol/L；Tin ion, antimony ion, cobalt ion mol ratio be 1:1:0.1；In the mixing salt solution that step (1) obtains, the concentration of graphite oxide is 0.5-2mg/mL。
Power ultrasonic in step (1) is 100-200W。
Reducing agent described in step (2) is hydrazine hydrate, ammonia, NaBH4With any one in HI；The concentration of described reducing agent is 0.1-2mol/L。
Solvent described in step (1) and step (2) is the solvents of any one or the two kinds mixing in deionized water, ethanol。
In step (3), the volume of liquid nitrogen is 0.5:1-2:1 with the volume ratio of turbid solution in step (2)。
In step (3), vacuum drying temperature is 50-80 DEG C, and the time is 10-24h。
In step (3), lyophilization temperature is-45 DEG C, and pressure is 0.37Pa, and the time is 40-70h。
Heating rate described in step (4) is 1-10 DEG C/min。
Embodiment 1
In the present embodiment, the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, comprise the following steps:
(1) SnCl of 0.001mol is weighed2, the SbCl of 0.001mol3, the CoCl of 0.0001mol2·6H2O and 0.0032molC6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution。By 0.1g graphite oxide ultrasonic disperse in mixing salt solution, wherein said ultrasonic power is 150W。
(2) the reducing agent NaBH of 0.1mol/L is regulated with NaOH4Aqueous solution so that it is pH >=12；NaBH by the 0.1mol/L of the 300mL of pH >=124Aqueous solution is slowly added dropwise in the mixing salt solution to step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, turbid solution is heated at 80 DEG C 5h。Wherein NaBH4The rate of addition of aqueous solution is 2mL/min, and mixing speed is 800r/min。
(3) it is 0.5:1 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2), after adding 200mL liquid nitrogen in the turbid solution of step (2), vacuum filtration, and the precipitate that sucking filtration obtained repeatedly wash with deionized water, dehydrated alcohol successively after carry out lyophilization, obtain SnSbCo/ Graphene precursor powder；Then precursor powder is placed in tube furnace, when argon shield, 300 DEG C of calcining at constant temperature 4h, obtain SnSbCo/ graphene composite negative pole。Wherein, cryodesiccated condition is 0.37Pa and-45 DEG C, and sublimation drying is 40h；The heating rate of tube furnace is 2 DEG C/min。
Reducing agent described in step (2) also can be selected for hydrazine hydrate, ammonia or HI。
In the present embodiment, the preparation method of graphite oxide is as follows: add 2g natural flake graphite and 2g sodium nitrate to being cooled in the concentrated sulphuric acid of 110mL of 0 DEG C in advance, continuously stirred 15-30min under condition of ice bath；Under condition of ice bath, it is slowly added to 12g potassium permanganate, stirs 20-40min, be then continuously stirred at room temperature 48h；It is slowly added to 184mL deionized water, stirs 150min；Add deionized water and 50mL hydrogenperoxide steam generator stirring 25min that 560mL temperature is 50-60 DEG C, obtain graphite oxide with dilute hydrochloric acid repeatedly centrifuge washing postlyophilization。The method preparing graphite oxide is not limited to this, and other can prepare the method for graphite oxide。
The present embodiment additionally provides a kind of sodium-ion battery using described SnSbCo/ graphene composite negative pole to prepare。Concrete, after SnSbCo/ graphene composite negative pole, conductive black, binding agent are 5:3:2 mix homogeneously according to mass ratio, Copper Foil is applied as the thin uniform layer that thickness is 100 μm, dry 12h, the circular electrode slice of roll-in rear cutout at 80 DEG C of vacuum。By circular electric pole piece, metallic sodium sheet, 1mol/L NaClO4/ EC/DEC electrolyte is assembled into sodium-ion battery。In the present embodiment, described binding agent is CMC binding agent, and the thickness after described thin layer roll-in is 70 μm, and the diameter of described circular electric pole piece is 18mm。
When preparing sodium-ion battery, described binding agent also can be selected for LA132 binding agent or polyvinylidene fluoride binding agent。
Embodiment 2
In the present embodiment, the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, comprise the following steps:
(1) stannous acetate of 0.02mol is weighed, the antimony acetate of 0.02mol, the cobaltous acetate of 0.002mol and 0.032molC6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution。By 0.05g graphite oxide ultrasonic disperse in mixing salt solution, wherein said ultrasonic power is 100W。
(2) the reducing agent NaBH of 1mol/L is regulated with NaOH4Aqueous solution so that it is pH >=12；NaBH by the 1mol/L of the 300mL of pH >=124Aqueous solution is slowly added dropwise in the mixing salt solution to step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, turbid solution is heated at 50 DEG C 12h。Wherein NaBH4The rate of addition of aqueous solution is 1mL/min, and mixing speed is 200r/min。
(3) it is 1:1 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2), after adding 400mL liquid nitrogen in the turbid solution of step (2), vacuum filtration, and the precipitate that sucking filtration obtained repeatedly wash with deionized water, dehydrated alcohol successively after carry out vacuum drying, obtain SnSbCo/ Graphene precursor powder；Then precursor powder is placed in tube furnace, when argon shield, 450 DEG C of calcining at constant temperature 2h, obtain SnSbCo/ graphene composite negative pole。Wherein, vacuum drying temperature is 50-80 DEG C, and drying time is 10-24h；The heating rate of tube furnace is 10 DEG C/min。
Reducing agent described in step (2) also can be selected for hydrazine hydrate, ammonia or HI。
The present embodiment additionally provides a kind of sodium-ion battery using described SnSbCo/ graphene composite negative pole to prepare。Concrete, after SnSbCo/ graphene composite negative pole, conductive black, binding agent are 8:1:1 mix homogeneously according to mass ratio, Copper Foil is applied as the thin uniform layer that thickness is 120 μm, dry 24h, the circular electrode slice of roll-in rear cutout at 50 DEG C of vacuum。By circular electric pole piece, metallic sodium sheet, 1mol/L NaClO4/EC/DEC electrolyte be assembled into sodium-ion battery。In the present embodiment, described binding agent is CMC binding agent, and the thickness after described thin layer roll-in is 35 μm, and the diameter of described circular electric pole piece is 18mm。
When preparing sodium-ion battery, described binding agent also can be selected for LA132 binding agent or polyvinylidene fluoride binding agent。
Embodiment 3
In the present embodiment, the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, comprise the following steps:
(1) SnCl of 0.05mol is weighed2, the SbCl of 0.05mol3, the CoCl of 0.005mol2·6H2O and 0.032molC6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution。By 0.2g graphite oxide ultrasonic disperse in mixing salt solution, wherein said ultrasonic power is 200W。
(2) the reducing agent NaBH of 2mol/L is regulated with NaOH4Aqueous solution so that it is pH >=12；NaBH by the 2mol/L of the 300mL of pH >=124Aqueous solution is slowly added dropwise in the mixing salt solution to step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, turbid solution is heated at 80 DEG C 1h。Wherein NaBH4The rate of addition of aqueous solution is 3mL/min, and mixing speed is 1000r/min。
(3) it is 2:1 according to the volume ratio of turbid solution in liquid nitrogen volume and step (2), after adding 800mL liquid nitrogen in the turbid solution of step (2), vacuum filtration, and the precipitate that sucking filtration obtained repeatedly wash with deionized water, dehydrated alcohol successively after carry out lyophilization, obtain SnSbCo/ Graphene precursor powder；Then precursor powder is placed in tube furnace, when argon shield, 200 DEG C of calcining at constant temperature 6h, obtain SnSbCo/ graphene composite negative pole。Wherein, cryodesiccated condition is 0.37Pa and-45 DEG C, and sublimation drying is 70h；The heating rate of tube furnace is 1 DEG C/min。
Reducing agent described in step (2) also can be selected for hydrazine hydrate, ammonia or HI。
The present embodiment additionally provides a kind of sodium-ion battery using described SnSbCo/ graphene composite negative pole to prepare。Concrete, after SnSbCo/ graphene composite negative pole, conductive black, binding agent are 6:2:2 mix homogeneously according to mass ratio, Copper Foil is applied as the thin uniform layer that thickness is 60 μm, dry 20h, the circular electrode slice of roll-in rear cutout at 60 DEG C of vacuum。By circular electric pole piece, metallic sodium sheet, 1mol/L NaClO4/ EC/DEC electrolyte is assembled into sodium-ion battery。In the present embodiment, described binding agent is CMC binding agent, and the thickness after described thin layer roll-in is 90 μm, and the diameter of described circular electric pole piece is 18mm。
When preparing sodium-ion battery, described binding agent also can be selected for LA132 binding agent or polyvinylidene fluoride binding agent。
Comparative example
The preparation method of SnSbCo/ Graphene negative material, comprises the following steps:
(1) SnCl of 0.001mol is weighed2, the SbCl of 0.001mol3, the CoCl of 0.0001mol2·6H2O and 0.032molC6H5Na3O7·2H2O, and be dissolved completely in the deionized water of 100mL, obtain mixing salt solution。By 0.05g graphite oxide ultrasonic disperse in mixing salt solution, wherein said ultrasonic power is 100W。
(2) NaBH of 0.1mol/L is regulated with NaOH4Aqueous solution so that it is pH >=12；NaBH by the 0.1mol/L of pH >=124Aqueous solution is slowly added dropwise in the mixing salt solution to step (1) and continuously stirred；After completion of dropwise addition, mixed solution is heated at 80 DEG C 5h。Wherein NaBH4The rate of addition of aqueous solution is 2mL/min, and mixing speed is 800r/min。
(3) by mixed solution vacuum filtration, and sucking filtration is precipitated after thing repeatedly washs with deionized water, dehydrated alcohol successively and carries out vacuum drying, obtain SnSbCo/ Graphene precursor powder；Then precursor powder is placed in tube furnace, when argon shield, 300 DEG C of calcining at constant temperature 4h, obtain SnSbCo/ Graphene negative material。Wherein, the heating rate of tube furnace is 2 DEG C/min。
Sodium-ion battery prepared by SnSbCo/ Graphene negative material prepared by a kind of comparative example of use。Concrete, after SnSbCo/ grapheme material, conductive black, binding agent are 5:3:2 mix homogeneously according to mass ratio, Copper Foil is applied as thin uniform layer, dry 12h, the circular electrode slice of roll-in rear cutout at 80 DEG C of vacuum。By circular electric pole piece, metallic sodium sheet, 1mol/L NaClO4/ EC/DEC electrolyte is assembled into sodium-ion battery。In the present embodiment, described binding agent is CMC binding agent, and the thickness after described thin layer roll-in is 70 μm, and the diameter of described circular electric pole piece is 18mm。
Measure of merit contrasts
Referring to Fig. 1 and Fig. 4, it is the XRD figure spectrum of the SnSbCo/ graphene composite negative pole prepared by embodiment 1 and comparative example respectively。The XRD figure of the SnSbCo/ graphene composite negative pole of embodiment 1 preparation is composed in the diffraction maximum that there is Graphene close to the position of 23 ° of angles of diffraction, and there is Sn-Sb, Co-Sb and Co-Sn alloy phase simultaneously。And the XRD figure of SnSbCo/ Graphene negative material prepared by comparative example is absent from the diffraction maximum of graphite oxide, surface NaBH in composing4Can abundant reduction-oxidation graphite。The position of the diffraction maximum of the main alloy phase Sn-Sb in SnSbCo/ graphene composite negative pole matches with JCPDS standard card (33-0118), there is Co-Sb and Co-Sn alloy phase simultaneously。
Please refer to Fig. 2-3 and 5-6, it is SEM and the TEM figure of the SnSbCo/ graphene composite negative pole prepared by embodiment 1 and comparative example respectively。It can be seen that the Graphene content in the SnSbCo/ graphene composite negative pole of embodiment 1 preparation is more from Fig. 2 and Fig. 3, it is possible to well wrap up alloying pellet, effectively reduce the reunion of alloying pellet。And from Fig. 5 and Fig. 6 it can be seen that SnSbCo/ graphene composite negative pole prepared by comparative example, Graphene content is few, and alloying pellet agglomeration is serious, it is impossible to be effectively embedded into graphene sheet layer。
Adopting the sodium-ion battery that the SnSbCo/ graphene composite negative pole prepared by embodiment 1 assembles is simulated battery 1, and adopting the sodium-ion battery that the SnSbCo/ graphene composite negative pole prepared by comparative example assembles is simulated battery 2。
The simulated battery 1 prepared and simulated battery 2 are carried out constant current charge-discharge test respectively, and test condition is: electric current density is 100mA/g；Voltage is 0-2.5V。Fig. 7 and Fig. 8 is the charge-discharge performance figure of simulated battery 1 and simulated battery 2 respectively。As shown in Figure 7, simulated battery 1 is under the electric current density of 100mA/g, and first discharge specific capacity is 998mAh/g, circulates 30 specific capacities and is positively retained at 600mAh/g, shows higher specific capacity and good cycle performance。And as shown in Figure 8, simulated battery 2 is under the electric current density of 100mA/g, first discharge specific capacity is 677mAh/g, and after circulating 30 times, specific capacity reduces to 464mAh/g, and capacity is relatively low and attenuation trend is obvious。
The charge-discharge performance of simulated battery 2 is SnSbCo/ graphene composite negative pole prepared by the comparative example that simulated battery 2 adopts than the main cause of simulated battery 1 difference, and Graphene content is few, and alloying pellet agglomeration is serious, it is impossible to be effectively embedded into graphene sheet layer。
Adopt the SnSbCo/ graphene composite negative pole of embodiment 2 preparation, equally because addition liquid nitrogen makes material internal steadiness increase, but the content minimizing compared with embodiment 1 due to graphite oxide, make its specific capacity increase but cyclical stability is not good enough, but be still better than in comparative example the performance of material。
Adopt the SnSbCo/ graphene composite negative pole of embodiment 3 preparation, compared with embodiment 1, a large amount of liquid nitrogen that add carry out cold quenching, promote that Graphene wraps up alloying pellet more securely further, can effectively reduce irreversible capacity, make follow-up charge and discharge cycles specific capacity increase。
Relative to prior art, the present invention passes through fabricated in situ technique, adopts titration reducing process to concurrently form a nanometer SnSbCo multi-nary alloy particles what prepare Graphene, is effectively improved material preparation efficiency。Add liquid nitrogen to cool down rapidly, make flake graphite alkene firmly wrap up SnSbCo alloying pellet by cold quenching technique, be effectively improved the structural stability of electrode material。Graphene content in the SnSbCo/ graphene composite negative pole that the present invention prepares is more, can be good at parcel alloying pellet, effectively reduce the reunion of alloying pellet, and the Graphene of high conductivity can improve the electric conductivity of electrode material on the one hand, can effectively alleviate the volumetric expansion that alloying pellet produces in charge and discharge process on the other hand。The material adopting the present invention assembles the sodium-ion battery obtained and has high charge-discharge specific capacity, good high rate performance and cycle performance。
The invention is not limited in above-mentioned embodiment, if to the various changes of the present invention or deformation without departing from the spirit and scope of the present invention, if these are changed and deform within the claim and the equivalent technologies scope that belong to the present invention, then the present invention is also intended to comprise these changes and deformation。
Claims (10)
1. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material, it is characterised in that: comprise the following steps:
(1) by pink salt, antimonic salt and salt solubility in solvent, mixing salt solution is obtained；By graphite oxide ultrasonic disperse in mixing salt solution；
(2) reducing agent is dissolved in solvent, obtains reducing solution；Reducing solution is added dropwise in the mixing salt solution of step (1) and continuously stirred；After completion of dropwise addition, obtain turbid solution, by turbid solution in 50-80 DEG C of stirring reaction；
(3) after adding the quick cold quenching of liquid nitrogen in the turbid solution of step (2), vacuum filtration, repeatedly washing postlyophilization or vacuum drying, obtain SnSbCo/ Graphene precursor powder；
(4) under inert gas shielding, calcining at constant temperature at precursor powder is warming up to 200-450 DEG C with certain heating rate, obtain SnSbCo/ graphene composite negative pole。
2. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 1, it is characterized in that: in step (1) described mixing salt solution, the concentration of pink salt is 0.01-0.5mol/L, the concentration of antimonic salt is 0.01-0.5mol/L, and the concentration of cobalt salt is 0.001-0.05mol/L；Tin ion, antimony ion, cobalt ion mol ratio be 1:1:0.1。
3. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 1, it is characterised in that: the volume adding liquid nitrogen in step (3) is 0.5:1-2:1 with the volume ratio of turbid solution in step (2)。
4. the liquid phase in-situ reducing-cold quenching preparation method of the composite negative pole material according to any claim in claim 1-3, it is characterised in that: in the mixing salt solution that step (1) obtains, the concentration of graphite oxide is 0.5-2mg/mL。
5. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 4, it is characterised in that: in step (2), the concentration of reducing solution is 0.1-2mol/L；Described reducing agent is hydrazine hydrate, ammonia, NaBH4With the one in HI。
6. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 4, it is characterised in that: power ultrasonic in step (1) is 100-200W；Rate of addition in step (2) is 1-3mL/min；Mixing speed in step (2) is 200-1000r/min。
7. the liquid phase in-situ reducing-cold quenching preparation method of composite negative pole material according to claim 4, it is characterised in that: described pink salt is stannous chloride or stannous acetate, and described antimonic salt is antimony chloride or antimony acetate, and described cobalt salt is cobaltous chloride or cobaltous acetate；Solvent described in step (1) and step (2) is the solvent of any one or the two mixing in deionized water, ethanol。
8. the preparation method of a sodium-ion battery, it is characterized in that: comprise the following steps: by SnSbCo/ graphene composite negative pole, conductive black, binding agent according to mass ratio for (50-80): (30-10): be coated on Copper Foil after (20-10) mix homogeneously, vacuum drying, cut into slices after roll-in, obtain circular electric pole piece；Electrode slice, metallic sodium sheet, electrolyte are assembled into sodium-ion battery；Described SnSbCo/ graphene composite negative pole is the SnSbCo/ graphene composite negative pole that in claim 1-7, preparation method described in any claim prepares。
9. the preparation method of sodium-ion battery according to claim 8, it is characterised in that: described binding agent is the one in LA132, polyvinylidene fluoride or CMC binding agent；Described coating thickness is 60-120 μm；The thickness of described roll-in is 35-90 μm。
10. a sodium-ion battery, it is characterized in that: include circular electric pole piece, metallic sodium sheet and electrolyte, described circular electric pole piece is (50-80) by SnSbCo/ grapheme material composite negative pole material, conductive black, binding agent according to mass ratio: (30-10): be coated on Copper Foil after (20-10) mix homogeneously, vacuum drying, after roll-in, section obtains, and described SnSbCo/ graphene composite negative pole is the SnSbCo/ graphene composite negative pole that in claim 1-7, preparation method described in any claim prepares。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118636.5A CN105702945B (en) | 2016-03-02 | 2016-03-02 | Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118636.5A CN105702945B (en) | 2016-03-02 | 2016-03-02 | Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105702945A true CN105702945A (en) | 2016-06-22 |
| CN105702945B CN105702945B (en) | 2018-08-28 |
Family
ID=56223829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610118636.5A Active CN105702945B (en) | 2016-03-02 | 2016-03-02 | Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105702945B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473663A (en) * | 2018-11-19 | 2019-03-15 | 北京航空航天大学 | A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony |
| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN113881399A (en) * | 2021-09-27 | 2022-01-04 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
| CN103762348A (en) * | 2014-01-25 | 2014-04-30 | 华南师范大学 | SnSbCu/MCMB/C core-shell structure serving as anode material of lithium ion battery and preparation method thereof |
-
2016
- 2016-03-02 CN CN201610118636.5A patent/CN105702945B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
| CN103762348A (en) * | 2014-01-25 | 2014-04-30 | 华南师范大学 | SnSbCu/MCMB/C core-shell structure serving as anode material of lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOQIU CHEN等: "Flake structured SnSbCo/MCMB/C composite as high performance anodes for lithium ion battery", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473663A (en) * | 2018-11-19 | 2019-03-15 | 北京航空航天大学 | A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony |
| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN113881399A (en) * | 2021-09-27 | 2022-01-04 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105702945B (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN100544081C (en) | A kind of nano lithium titanate and with the preparation method of the compound of titanium dioxide | |
| CN103219168B (en) | A kind of Li 4ti 5o 12/ graphene combination electrode material and preparation method thereof | |
| CN103682332B (en) | Compound negative material of a kind of lithium ion battery and preparation method thereof and lithium ion battery | |
| CN104051729B (en) | NiFe for cathode of lithium battery2o4the preparation method of/graphene composite material | |
| CN104966824A (en) | Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof | |
| CN102386410A (en) | Lithium vanadium phosphate/graphene composite material and preparation method thereof | |
| CN101877405A (en) | Preparation method of lithium titanate-graphene combination electrode material | |
| CN106450305B (en) | A kind of preparation method of lithium ion battery negative material CoP/C | |
| CN107069001B (en) | Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof | |
| CN105428618B (en) | A kind of preparation method and applications of core-shell type carbon-clad metal sulfide nano-complex particle | |
| CN108598444B (en) | Vanadium trioxide/graphene composite negative electrode material of lithium ion battery and preparation method | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN109616331B (en) | Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
| CN104852028A (en) | Lithium titanate/graphene composite cathode material for lithium ion battery | |
| CN104167540A (en) | Negative electrode active material and preparation method thereof and lithium ion battery | |
| CN104617280A (en) | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof | |
| CN101355150B (en) | Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN105609772A (en) | Method for preparing N, S-codoped graphene cathode material for lithium-sulfur battery by microwave method | |
| CN103236519A (en) | Porous carbon base monolith composite material for lithium ion battery, and preparation method thereof | |
| CN105702956A (en) | Negative material for sodium-ion battery and preparation method of negative material | |
| CN105702958A (en) | SnO2 quantum dot solution and preparation method and application of composite material thereof | |
| Du et al. | Encapsulating yolk-shelled Si@ Co9S8 particles in carbon fibers to construct a free-standing anode for lithium-ion batteries | |
| CN105552337A (en) | MoS2/C/LiVPO4F composite anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |