CN108735991A - A kind of kalium ion battery negative material and preparation method and electrolyte - Google Patents

A kind of kalium ion battery negative material and preparation method and electrolyte Download PDF

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CN108735991A
CN108735991A CN201810427488.4A CN201810427488A CN108735991A CN 108735991 A CN108735991 A CN 108735991A CN 201810427488 A CN201810427488 A CN 201810427488A CN 108735991 A CN108735991 A CN 108735991A
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composite material
doped graphene
graphene composite
dimensional porous
porous nitrogen
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CN108735991B (en
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李平
韩坤
王伟
刘志伟
刘颖
赵汪
安富强
曲选辉
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University of Science and Technology Beijing USTB
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • 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
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02E60/10—Energy storage using batteries

Abstract

A kind of kalium ion battery negative material and preparation method and electrolyte, belong to field of chemical power source.The material composition of negative material is：60%~95% Fe-base compound modifies three-dimensional porous nitrogen-doped graphene composite material, 2%~30% conductive agent, 3%~10% Kynoar (PVDF) binder；The Fe-base compound modifies three-dimensional porous nitrogen-doped graphene composite material as any one in the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite, di-iron trioxide nano-particle modified three-dimensional porous nitrogen-doped graphene composite material and ferrous disulfide.Kalium ion battery negative material prepared by the present invention has stable frame structure, big specific surface area and nano-particle modified, electrochemical performance；And abundant raw material, manufacturing cost is low, easy large-scale production, has very important industrial applications foreground.

Description

A kind of kalium ion battery negative material and preparation method and electrolyte
Technical field
The invention belongs to electrochemical fields, and in particular to a kind of kalium ion battery three-dimensional porous nitrogen of Fe-base compound modification Doped graphene negative material and preparation method and electrolyte improve the electricity of electrode material especially by the optimization of electrolyte Chemical property.
Background technology
With energy environment issues become increasingly conspicuous and the cost of lithium ion battery rises steadily, there is an urgent need to develop new The energy storage technology of type.Kalium ion battery is due to many advantages and with huge development prospect.First, potassium resource reserves are rich Richness, it is at low cost；Secondly, compared with otheralkali metal ion, weaker lewis acid property makes K+In electrolyte and electrolysis Liquid and electrode interface all have larger transfer number and mobility；Finally, K+The standard electrode EMF ratio Na of/K+/ Na is lower, with Li+/ Li is closer (- 2.93V, -2.71V, -3.04V, Vs.SHE), it means that kalium ion battery will have higher work Voltage and energy density have very big foreground in following energy storage field.Currently, related kalium ion battery negative material Report focuses mostly in traditional carbon-based material, however due to K+Size is largerIt can cause larger volume during deintercalation Expansion, causes its cycle performance very poor；In addition, its specific capacity is also to be improved.Therefore, a kind of height ratio capacity, long circulating are developed The negative material in service life is particularly significant for the development of kalium ion battery.
Invention content
In view of the above problems, the present invention is with carbonates electrolyte (such as 1mol/L KPF6/ EC/DEC) and ether Class electrolyte (such as 1mol/L KCF3SO3/ DGM) it is electrolyte, three-dimensional porous nitrogen-doped graphene is modified using Fe-base compound Composite material is as kalium ion battery negative material.Three-dimensional grapheme have stable frame structure, big specific surface area and Excellent electronics and ionic conduction performance, storage potassium mechanism includes flooding mechanism and capacitance mechanism, can improve high rate performance and follow Ring performance；In addition the modification of cementite, iron oxide, vulcanization iron nano-particle can further increase the capacity of composite material.Through Literature survey does not modify three-dimensional porous nitrogen-doped graphene composite material about Fe-base compound so far and is used as potassium ion The report of cell negative electrode material.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of kalium ion battery negative material, by the material composition of following mass fraction：60%~95% iron-based It closes object and modifies three-dimensional porous nitrogen-doped graphene composite material, 2%~30% conductive agent, 3%~10% Kynoar (PVDF) binder, the mass fraction are the mass fractions relative to negative material gross mass.The Fe-base compound is repaiied It is that the nano-particle modified three-dimensional porous nitrogen-doped graphene of cementite is compound to adorn three-dimensional porous nitrogen-doped graphene composite material The nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of material, di-iron trioxide, ferrous disulfide nano particle are repaiied Any one of the three-dimensional porous nitrogen-doped graphene composite material of decorations.
Further, the conductive agent is one or more mixtures in Ketjen black, acetylene black or super P.
Further, Fe-base compound is modified into three-dimensional porous nitrogen-doped graphene composite material, conductive agent and binder Kynoar (PVDF) is according to 7:2:1 ratio mixing is added appropriate N-Methyl pyrrolidone (NMP) after grinding uniformly and is made Slurry is uniformly coated on copper foil, after 80~120 DEG C of 8~12h of vacuum drying, is cut out slice and is obtained negative electricity pole piece.
Further, the electrolyte to match with the kalium ion battery negative material, including：Electrolyte is sylvite, solvent Including carbonate-based solvent and ether-based solvent.Wherein the mass fraction of solvent is 60%~90%, and the mass fraction of sylvite is 10%~40%.
Further, the sylvite is trifluoromethane sulfonic acid potassium (KCF3SO3), Potassium Hexafluorophosphate (KPF6), potassium hyperchlorate (KClO4), any one or arbitrary combination in double trifluoromethanesulfonimide potassium (KTFSI).
Further, the carbonate-based solvent is ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), any one in methyl ethyl carbonate (EMC), diethyl carbonate (DEC) or the arbitrary combination between them；Described Ether-based solvent is any one in diethylene glycol dimethyl ether (DGM), glycol dimethyl ether (DME).
Further, the sylvite substance withdrawl syndrome is 0.5~2mol/L.
Advantages of the present invention：
(1) Fe-base compound provided by the invention modifies the abundant raw material of three-dimensional porous nitrogen-doped graphene composite material, Preparation process is simple, at low cost, with short production cycle, can realize prepare with scale.
(2) Fe-base compound provided by the invention modifies three-dimensional porous nitrogen-doped graphene composite material, has stabilization Graphene film is fixed support and forms three-dimensional grapheme frame by three-dimensional graphite skeleton structure, graphite skeleton；In potassium ion deintercalation Cheng Zhong, three-dimensional frame structure can keep stable；Meanwhile three-dimensional graphite skeleton can be used as conductive network, improve electronics Efficiency of transmission；In addition, composite material also has big specific surface area, more reaction active sites can be provided for electrochemical reaction Point.
(3) kalium ion battery that kalium ion battery negative material provided by the invention is assembled into, since negative material has Stable three-dimensional frame structure, graphite skeleton as conductive network transmit electronics, big specific surface area for adsorption to K+, and There are N doping element and Fe-base compound are nano-particle modified, thus with high specific discharge capacity, excellent forthright again Energy and cycle performance.To have a good application prospect.
(4) present invention can be directed to different Fe-base compounds and modify three-dimensional porous nitrogen-doped graphene negative material, Electrolyte with heterogeneity, to effectively filter out the electrolyte haveing excellent performance；And further pass through bath composition Optimization promotes the chemical property of composite negative pole material.
(5) kalium ion battery electrolyte provided by the invention have low viscosity, low toxicity and wider electrochemical window and Temperature range not only has good chemical property using this kalium ion battery electrolyte, and safety is also very good, tool There is wide application market.
Description of the drawings
Fig. 1 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (a) of the cementite of the invention prepared The XRD spectrum of nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (b) with ferrous disulfide.
Fig. 2 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (a) of the cementite of the invention prepared The FESEM photos of nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (b) with ferrous disulfide.
Fig. 3 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (a) of the cementite of the invention prepared The AFM photos of nano-particle modified three-dimensional porous nitrogen-doped graphene composite material (b) with ferrous disulfide.
Fig. 4 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite prepared by the present invention XPS-N1s collection of illustrative plates.
Fig. 5 is that the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite is negative as kalium ion battery Pole material the 1st, 2,5,50,100 circle charging and discharging curve figure under the current density of 500mA/g.Electrolyte group becomes 1mol/L KPF6/EC/DEC。
Fig. 6 is that the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite is negative as kalium ion battery The high rate performance figure of pole material.Electrolyte group becomes 1mol/L KPF6/EC/DEC。
Fig. 7 is that the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite is negative as kalium ion battery Pole material is in the cycle performance figure of 500mA/g, and electrolyte group is as 1mol/L KPF6/EC/DEC。
Fig. 8 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of ferrous disulfide as kalium ion battery When negative material, 1mol/L KPF are respectively adopted6/ EC/DEC and 1mol/L KCF3SO3The potassium ion electricity of/DGM electrolyte assembling Cycle performance figure of the pond in 50mA/g.
Specific implementation mode
It in order to make the purpose , technical scheme and advantage of the present invention be clearer, below will be by attached drawing and specifically real Applying example, invention is further described in detail.
Embodiment one
In mass ratio 1:1.5 weigh polyvinylpyrrolidonepowder powder and nine water ferric nitrates, by nine water ferric nitrates and polyethylene Pyrrolidones dissolves respectively is made into mixed solution ultrasonic agitation 10min in deionized water, and mixed solution is then placed in air blast 80 DEG C of heat preservations are until be completely dried in drying box, then the product after drying is ground into powder and powder is transferred in crucible, Crucible is placed in tube furnace in N2700 DEG C are heated to the heating rate of 5 DEG C/min in atmosphere, keeps the temperature 1h, waits for that tube furnace cools down Black foam shape product is collected afterwards, obtains the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite.It takes Then the appropriate nano-particle modified three-dimensional porous nitrogen-doped graphene composite powder of cementite is set crucible in crucible In tube furnace airflow downstream position；It takes excessive sublimed sulfur in another crucible, crucible is placed in air-flow upstream position；? 300 DEG C are heated to the heating rate of 2 DEG C/min in the argon stream atmosphere of 100sccm/min, keeps the temperature 2h, waits for that tube furnace cools down Foam-like product is collected afterwards, obtains the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of ferrous disulfide.
Fig. 1 is the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of the cementite prepared by embodiment one The XRD diagram of nano-particle modified three-dimensional porous nitrogen-doped graphene composite material with ferrous disulfide, reference standard PDF cards can To find out, object is respectively mutually the compound phase of cementite and graphene, ferrous disulfide and graphene.Fig. 2 is prepared by embodiment one Cementite it is nano-particle modified three-dimensional porous nitrogen-doped graphene composite material and ferrous disulfide it is nano-particle modified three The FESEM figures of porous nitrogen-doped graphene composite material are tieed up, as can be seen from Figure, two kinds of composite materials of synthesis are three-dimensional Porous structure, for graphene film by three-dimensional graphite skeletal support, pore diameter is 5~10 μm.Fig. 3 is the carbon prepared by embodiment one The three-dimensional that the three-dimensional porous nitrogen-doped graphene composite material and ferrous disulfide of change iron nano-particle modification are nano-particle modified is more The AFM of hole nitrogen-doped graphene composite material schemes, as can be seen from Figure, prepared graphene thickness be respectively 1.5nm and 1.4nm, about 4 layer graphene thickness.Fig. 4 is that the nano-particle modified three-dimensional porous nitrogen-doped graphene of prepared cementite is multiple The presence of the XPS-N1s swarming fitting results of condensation material, the peak shows that N atoms are successfully entrained in graphene base body, and graphite There are the nitrogen of type in 3, i.e. pyridine nitrogen in alkene, graphite nitrogen and pyrroles's nitrogen.N doping has the electric conductivity of material and carries Height, and it is also beneficial to the absorption of potassium ion, improve battery performance.
Embodiment two
By cementite nano-particle modified three-dimensional porous nitrogen-doped graphene composite material, conductive agent Ketjen black and bonding Agent Kynoar (PVDF) in mass ratio 7:2:1 mixing is added appropriate N-Methyl pyrrolidone (NMP) after grinding uniformly and is made Slurry is uniformly coated on copper foil.After 100 DEG C of vacuum drying 10h, the electrode slice that diameter 10mm is cut into slicer is standby With.It is to electrode with metallic potassium piece, glass fibre is diaphragm, 1mol/L KPF6/ EC/DEC is electrolyte, in argon gas protection CR2032 type button cells are assembled into glove box.Battery pack stands 12h after installing, with LAND CT2001A battery test systems Constant current charge-discharge test is carried out, test voltage is 0.01~2.5V.
Fig. 5 be the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of prepared cementite as potassium from Charging and discharging curve figure of the sub- cell negative electrode material under 500mA/g current densities, first circle specific discharge capacity are 300mAh/g, charging Specific capacity 217mAh/g.After the activation of preceding 2 circle, charge and discharge tend towards stability substantially, and charge and discharge cycles curve is kissed substantially within 100 weeks It closes.Fig. 6 is its high rate performance figure, and under the current density of 50,100,200,500 and 1000mA/g, sample shows respectively The specific capacity of 350,310,252,226 and 195mAh/g.When current density resets back 50mA/g, specific capacity is still kept 312mAh/g illustrates excellent forthright again of the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of cementite Energy.Fig. 7 is the specific capacity variation during its 500 weeks charge and discharge cycles, and specific capacity still maintains 210mAh/ after recycling 500 weeks G illustrates that the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of prepared cementite has good cycle Stability, and also indicate that the material can carry out high rate charge-discharge, there is very big application prospect.
Embodiment three
By cementite nano-particle modified three-dimensional porous nitrogen-doped graphene composite material, conductive agent Ketjen black and bonding Agent Kynoar (PVDF) in mass ratio 6:3:1 mixing is added appropriate N-Methyl pyrrolidone (NMP) after grinding uniformly and is made Slurry is uniformly coated on copper foil.After 100 DEG C of vacuum drying 10h, the electrode slice that diameter 10mm is cut into slicer is standby With.It is to electrode with metallic potassium piece, glass fibre is diaphragm, 1mol/L KPF6/ EC/DEC is electrolyte, in argon gas protection CR2032 type button cells are assembled into glove box.Battery pack stands 12h after installing, with LAND CT2001A battery test systems Constant current charge-discharge test is carried out, test voltage is 0.01~2.5V.
Example IV
By cementite nano-particle modified three-dimensional porous nitrogen-doped graphene composite material, conductive agent Ketjen black and bonding Agent Kynoar (PVDF) in mass ratio 8:1:1 mixing is added appropriate N-Methyl pyrrolidone (NMP) after grinding uniformly and is made Slurry is uniformly coated on copper foil.After 100 DEG C of vacuum drying 10h, the electrode slice that diameter 10mm is cut into slicer is standby With.It is to electrode with metallic potassium piece, glass fibre is diaphragm, 1mol/L KPF6/ EC/DEC is electrolyte, in argon gas protection CR2032 type button cells are assembled into glove box.Battery pack stands 12h after installing, with LAND CT2001A battery test systems Constant current charge-discharge test is carried out, test voltage is 0.01~2.5V.
Embodiment five
By the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of ferrous disulfide, conductive agent Ketjen black and glue Tie agent Kynoar (PVDF) in mass ratio 7:2:Appropriate N-Methyl pyrrolidone (NMP) system is added in 1 mixing after grinding uniformly At slurry, it is uniformly coated on copper foil.After 100 DEG C of vacuum drying 10h, the electrode slice of diameter 10mm is cut into slicer It is spare.It is to electrode with metallic potassium piece, glass fibre is diaphragm, 1mol/L KPF6/ EC/DEC is electrolyte, is protected in argon gas Glove box in be assembled into CR2032 type button cells.Battery pack stands 12h after installing, with LAND CT2001A battery testings system System carries out constant current charge-discharge test, and test voltage is 0.8~3.0V.
Embodiment six
By the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of ferrous disulfide, conductive agent Ketjen black and glue Tie agent Kynoar (PVDF) in mass ratio 7:2:Appropriate N-Methyl pyrrolidone (NMP) system is added in 1 mixing after grinding uniformly At slurry, it is uniformly coated on copper foil.After 100 DEG C of vacuum drying 10h, the electrode slice of diameter 10mm is cut into slicer It is spare.It is to electrode with metallic potassium piece, glass fibre is diaphragm, 1mol/L KCF3SO3/ DGM is electrolyte, in argon gas protection CR2032 type button cells are assembled into glove box.Battery pack stands 12h after installing, with LAND CT2001A battery test systems Constant current charge-discharge test is carried out, test voltage is 0.8~3.0V.
Fig. 8 be the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of prepared ferrous disulfide as potassium from When sub- cell negative electrode material, using different electrolytes assembling kalium ion battery 50mA/g cycle performance figure.As seen from the figure, When using 1mol/L KPF6When/EC/DEC is electrolyte, though starting specific capacity up to 374mAh/g, decaying is very fast, cycle Specific capacity is 52.4mAh/g after 200 circles；And use 1mol/L KCF3SO3When/DGM is electrolyte, first circle specific discharge capacity is up to For 420mAh/g, specific capacity still maintains 385mAh/g after recycling 200 weeks.Illustrate that prepared ferrous disulfide is nano-particle modified Three-dimensional porous nitrogen-doped graphene composite negative pole material and 1mol/L KCF3SO3/ DGM electrolyte matchings are more preferable, therefore have There is good cyclical stability.
The electrolyte to match with the kalium ion battery negative material disclosed in the embodiment of the present invention, including, carbonic ester Based solvent, ether-based solvent and sylvite；Wherein the mass fraction of solvent is 60%~90%, the mass fraction of sylvite is 10%~ 40%.Wherein the substance withdrawl syndrome of sylvite is 0.5~2mol/L.Carbonate-based solvent packet wherein in carbonate group electrolyte Include ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) any one in or the arbitrary combination between them；Ether-based solvent is diethylene glycol dimethyl ether (DGM), glycol dinitrate Any one in ether (DME).Sylvite is trifluoromethane sulfonic acid potassium (KCF3SO3), Potassium Hexafluorophosphate (KPF6), potassium hyperchlorate (KClO4) in any one or arbitrary combination.Therefore, carbonate-based solvent, ether-based solvent and sylvite are not limited to embodiment Given in the specific bath composition that goes out.The above components are used in technical solution of the present invention, can reach same technology Effect.Therefore embodiment provided by the present invention is only used for the further explanation done to the present invention, so that this field skill Art personnel are it will be appreciated that embodiments of the present invention and effect, to the concrete component and raw material gone out given in embodiment, not pair The limitation of the scope of the present invention.
It will be appreciated that the present invention is not limited to embodiment here, those skilled in the art's announcement according to the present invention, by this The improvement and modification that inventive concept is made all should be within protection scope of the present invention.

Claims (8)

1. a kind of kalium ion battery negative material, it is characterised in that：The material composition of negative material is：60%~95% iron Based compound modifies three-dimensional porous nitrogen-doped graphene composite material, 2%~30% conductive agent, 3%~10% poly- inclined fluorine Ethylene (PVDF) binder；It is cementite nanometer that the Fe-base compound, which modifies three-dimensional porous nitrogen-doped graphene composite material, Three-dimensional porous nitrogen-doped graphene composite material, the nano-particle modified three-dimensional porous N doping stone of di-iron trioxide of grain modification Any one in black alkene composite material and the nano-particle modified three-dimensional porous nitrogen-doped graphene composite material of ferrous disulfide.
2. a kind of preparation method of kalium ion battery negative material as described in claim 1, it is characterised in that：Preparation process For：
Nine water ferric nitrates and polyvinylpyrrolidone dissolving are stirred by ultrasonic are uniformly mixed in deionized water by step 1), then It is dry, grind into powder；By gained powder in inert protective atmosphere heating and thermal insulation, obtain cementite it is nano-particle modified three Tie up porous nitrogen-doped graphene composite material；
Step 2), product in step 1) is carried out in air atmosphere be thermally treated resulting in di-iron trioxide it is nano-particle modified three Porous nitrogen-doped graphene composite material is tieed up, then is vulcanized by chemical vapour deposition technique, ferrous disulfide nano particle is obtained The three-dimensional porous nitrogen-doped graphene composite material of modification；Step 1) and step 2) products therefrom are referred to as Fe-base compound modification three Tie up porous nitrogen-doped graphene composite material；
The Fe-base compound of preparation is modified three-dimensional porous nitrogen-doped graphene composite material and conductive agent, binder by step 3) Kynoar (PVDF), which is added appropriate N-Methyl pyrrolidone after mixed grinding in proportion and is slurried, is uniformly coated on copper foil On, cathode use is can be used as after dry.
3. the preparation method of kalium ion battery negative material according to claim 2, it is characterized in that being：The conduction Agent is one or more mixtures in Ketjen black, acetylene black or super P.
4. the preparation method of kalium ion battery negative material according to claim 2, it is characterised in that：Fe-base compound The mixed proportion for modifying three-dimensional porous nitrogen-doped graphene composite material, conductive agent and binder Kynoar (PVDF) is 7: 2:1 drying temperature is 80~120 DEG C, is dried in vacuo 8~12h.
5. a kind of electrolyte to match with kalium ion battery negative material described in claim 1, it is characterised in that：Electrolysis Matter is sylvite, and solvent includes carbonate-based solvent and ether-based solvent, and the wherein mass fraction of solvent is 60%~90%, sylvite Mass fraction is 10%~40%.
6. electrolyte according to claim 5, it is characterised in that：The sylvite is trifluoromethane sulfonic acid potassium (KCF3SO3), Potassium Hexafluorophosphate (KPF6), potassium hyperchlorate (KClO4), it is arbitrary in double trifluoromethanesulfonimide potassium (KTFSI) A kind of or arbitrary combination.
7. electrolyte according to claim 5, it is characterised in that：The carbonate-based solvent is ethylene carbonate (EC), any one in propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) Kind or the arbitrary combination between them；The ether-based solvent is in diethylene glycol dimethyl ether (DGM), glycol dimethyl ether (DME) Any one.
8. electrolyte according to claim 5, it is characterised in that：The sylvite substance withdrawl syndrome is 0.5~2mol/ L。
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