CN110416528A - A kind of kalium ion battery - Google Patents

A kind of kalium ion battery Download PDF

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Publication number
CN110416528A
CN110416528A CN201810393953.7A CN201810393953A CN110416528A CN 110416528 A CN110416528 A CN 110416528A CN 201810393953 A CN201810393953 A CN 201810393953A CN 110416528 A CN110416528 A CN 110416528A
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CN
China
Prior art keywords
ion battery
kalium ion
battery according
kalium
electrolyte
Prior art date
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Pending
Application number
CN201810393953.7A
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Chinese (zh)
Inventor
李文武
刘国平
李艳红
郭再萍
张文超
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Guangdong University of Technology
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Guangdong University of Technology
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Priority to CN201810393953.7A priority Critical patent/CN110416528A/en
Publication of CN110416528A publication Critical patent/CN110416528A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to electrochemical fields, and in particular to a kind of kalium ion battery.Kalium ion battery provided by the invention, including anode, cathode and electrolyte；The anode includes kalium ion battery positive electrode；The anode active material layer of the cathode is GeP5Compound.The problem of it is low and elemental phosphorous low with phosphide conductivity that the invention solves the carbon based negative electrodes material specific capacity in kalium ion battery in the prior art, poor circulation provides a kind of novel kalium ion battery negative electrode material.

Description

A kind of kalium ion battery
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of kalium ion battery.
Background technique
With the increasingly increase to electric car and large-scale energy storage device demand, in recent years, lithium ion battery is portable It has occupied an leading position in equipment and electric car.But since elemental lithium resource is limited, widen cost-effective battery Substitute is increasingly becoming trend.Sodium and potassium are because its property is similar to lithium and rich reserves attract attention in the soil. However, sodium-ion battery since energy density is lower, often makes the operating voltage of battery insufficient.In the application of kalium ion battery In, carbon based negative electrodes material is widely used in kalium ion battery cathode because of its excellent cycle performance and reversible storage potassium capability In.However, since its excessively high operating voltage leads to the factors such as low specific capacity, low energy densities, in terms of industrial application There are still obstacles.Substitution of the phosphorus as a kind of negative electrode material, since its higher theoretical specific capacity (2594mAh/g) is considered With very extensive utilization prospect.But elemental phosphorous conductivity is low, storage potassium volume expansion is big, in order to overcome these disadvantages, Alloy-based phosphide such as NiP2,Se4P4,Sn4P3And SnP3, because its compound metallicity and concerted reaction mechanism the features such as It is introduced in kalium ion battery negative electrode material, but since its phosphorus element content is lower, makes the potassium ion electricity using it as cathode The capacitance in pond is low and cycle performance is bad.
Summary of the invention
In view of this, solving the carbon in kalium ion battery in the prior art the present invention provides a kind of kalium ion battery Base negative electrode material is since its excessively high operating voltage causes specific capacity too low with energy density, and due in alloy-based phosphide The technical problem that the too low capacitance for leading to kalium ion battery of P elements is low and cycle performance is bad.
The present invention is supplied to a kind of kalium ion battery, including anode, cathode and electrolyte；
The anode includes kalium ion battery positive electrode；
The anode active material layer of the cathode is GeP5Compound.
Preferably, the electrolyte of the electrolyte is fluorine sulfimide potassium.
Preferably, the solvent of the electrolyte includes ethylene carbonate and/or ethylene carbonate.
Preferably, the GeP5The preparation method of compound includes that germanium powder and phosphorus powder 1:5 mixing in molar ratio are carried out ball Mill.
Preferably, the ratio of grinding media to material of the ball milling is 20:1.
Preferably, the time of the ball milling is 5~10h.
Preferably, the revolving speed of the ball milling is 900~1200r/min.
Preferably, the cathode further includes binder and collector, and the anode active material layer passes through the binder It is bonded on the surface of the collector.
Preferably, the binder is selected from Kynoar, polytetrafluoroethylene (PTFE), Lithium polyacrylate, polyvinyl alcohol, carboxymethyl Sodium cellulosate, polyurethane or butadiene-styrene rubber.
It is furthermore preferred that the binder is Lithium polyacrylate.
Preferably, the collector is selected from copper foil, aluminium foil, nickel foil, copper mesh, aluminium net or nickel screen.
It is furthermore preferred that the collector is copper foil.
The present invention provides a kind of kalium ion battery, anode active material layer GeP5Compound, due to GeP5Middle P member Cellulose content is higher, each phosphonium ion (P3-) 3 potassium ion (K can be stored+), so that GeP5Energy when as kalium ion battery cathode More potassium ions are stored, it can when serving as kalium ion battery cathode in conjunction with its special layer structure and metallic conductivity To significantly improve kalium ion battery theoretical specific capacity and reactivity.Further, since P elements have stronger electronegativity, make GeP5With higher storage potassium activity, the performance of battery can be further improved.
It is of the invention the experimental results showed that, GeP prepared by the present invention5Compound purity is higher, and as kalium ion battery When negative electrode active material, discharge capacity is 1400mAh/g for the first time, after 2000 circles are recycled under the high current density of 500mA/g, It stores up potassium capacity and remains at 200mAh/g, and capacity retention ratio is higher, illustrates that the kalium ion battery has good storage potassium performance With cyclical stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described.
Fig. 1 is GeP of the present invention5The X-ray diffractogram of compound；
Fig. 2 is GeP of the present invention5The scanning electron microscope (SEM) photograph of compound；
Fig. 3 is GeP of the present invention5The transmission electron microscope picture of compound；
Fig. 4 is the cycle performance test chart of the embodiment of the present invention 2.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, Other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to guarantor of the present invention The range of shield.
The present invention provides a kind of kalium ion battery negative electrode materials, and are made into cathode and apply in kalium ion battery, Solve causes the technology that the capacitance of kalium ion battery is low and cycle performance is bad to be asked since P elements are too low in the prior art Topic.
It is negative to lithium ion/sodium-ion battery provided by the present application below with reference to embodiment for a further understanding of the application Pole material is specifically described.
Embodiment 1
In molar ratio 1:5 by purity be 99.9% germanium powder and purity be 99.8% phosphorus powder be added in ball grinder, adopt With the ratio of grinding media to material of 20:1, under the revolving speed of 900~1200r/min, ball milling obtained GeP after 5-10 hours5Compound, Fig. 1 GeP5 The X-ray diffractogram of compound shows it can be seen from the figure that its diffraction maximum is corresponding with standard card (PDF-24-0455) Synthesized substance is GeP5And purity is higher.
Fig. 2 is GeP5The scanning electron microscope (SEM) photograph of compound, Fig. 3 GeP5The transmission electron microscope picture of compound, can from Fig. 2 and Fig. 3 To find out the GeP of synthesis5Compound is block materials, and partial size is smaller, about 500nm, and it is swollen to be conducive to volume after alleviating storage potassium Stress brought by swollen, to prevent material breaks.
Embodiment 2
Using Lithium polyacrylate as binder, conductive black is as conductive agent, and copper foil is as collector, by what is be prepared GeP5Compound is bonded on the surface of copper foil as anode active material layer by Lithium polyacrylate, and kalium ion battery is made Cathode.In the electrochemical property test of kalium ion battery, GeP is made in above-mentioned kalium ion battery cathode and metallic potassium5- K button Formula battery, and respectively with Potassium Hexafluorophosphate-ethylene carbonate/diethyl carbonate (KPF6- EC/DEC), double fluorine sulfimide potassium- Ethylene carbonate/ethylene carbonate (KFSI-EC/DEC), Potassium Hexafluorophosphate-ethylene carbonate/diethyl carbonate/fluoro carbonic acid Vinyl acetate (KPF6- EC/DEC/FEC), double fluorine sulfimides potassium-ethylene carbonate/ethylene carbonate/fluorinated ethylene carbonate (KFSI-EC/DEC/FEC) its cycle performance is tested for electrolyte.
Fig. 4 is the cycle performance test chart of the embodiment of the present invention 2.It can be seen from the figure that being mixed with fluoro ethylene carbonate The electrode of the electrolyte of ester (FEC) its specific capacity is lower for the first time, and circulation 800~1000 circle after decay rapidly.Show fluoro The addition of ethylene carbonate (FEC) will lead to the generation of excess fluoride to cause biggish irreversible capacity.And it is being not added In the case where entering fluorinated ethylene carbonate FEC, in electrolyte Potassium Hexafluorophosphate-ethylene carbonate/diethyl carbonate (KPF6-EC/ DEC in), there is unstable variation in battery capacity of battery after the circle of circulation 200, this shows GeP5Electrode is in Surface Creation In the case where unstable SEI film, cyclical stability is deteriorated, and excessive side reaction has occurred so as to cause battery, causes battery Inactivation.
When the kalium ion battery is using KFSI-EC/DEC as electrolyte, first circle charge and discharge are under the current density of 50mA/g It carrying out, discharge capacity is 1400mAh/g for the first time, under the current density for being up to 500mA/g later after 2000 circle of circulation, storage Potassium capacity is maintained at 200mAh/g, shows electrode surface can be made to form uniform solid when using KFSI as electrolyte Electrolyte interface layer, to inhibit side reaction, this makes GeP5Compound has when using as kalium ion battery negative electrode material There are good storage potassium performance and cyclical stability.
Obviously, embodiments as described above is only a part of the embodiment of the present invention, instead of all the embodiments.Base Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its His embodiment, shall fall within the protection scope of the present invention.

Claims (10)

1. a kind of kalium ion battery, which is characterized in that including anode, cathode and electrolyte；
The anode includes kalium ion battery positive electrode；
The anode active material layer of the cathode is GeP5Compound.
2. a kind of kalium ion battery according to claim 1, which is characterized in that the electrolyte of the electrolyte is fluorine sulphonyl Imines potassium.
3. a kind of kalium ion battery according to claim 1, which is characterized in that the solvent of the electrolyte includes carbonic acid second Enester and/or ethylene carbonate.
4. a kind of kalium ion battery according to claim 1, which is characterized in that the GeP5The preparation method packet of compound Include that 1:5 is mixed and carried out ball milling in molar ratio by germanium powder and phosphorus powder.
5. a kind of kalium ion battery according to claim 4, which is characterized in that the ratio of grinding media to material of the ball milling is 20:1.
6. a kind of kalium ion battery according to claim 4, which is characterized in that the time of the ball milling is 5~10h.
7. a kind of kalium ion battery according to claim 4, which is characterized in that the revolving speed of the ball milling be 900~ 1200r/min。
8. a kind of kalium ion battery according to claim 1, which is characterized in that the cathode further includes binder and afflux Body, the anode active material layer are bonded on the surface of the collector by the binder.
9. a kind of kalium ion battery according to claim 8, which is characterized in that the binder be selected from Kynoar, Polytetrafluoroethylene (PTFE), Lithium polyacrylate, polyvinyl alcohol, sodium carboxymethylcellulose, polyurethane or butadiene-styrene rubber.
10. a kind of kalium ion battery according to claim 8, which is characterized in that the collector be selected from copper foil, aluminium foil, Nickel foil, copper mesh, aluminium net or nickel screen.
CN201810393953.7A 2018-04-27 2018-04-27 A kind of kalium ion battery Pending CN110416528A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015034315A (en) * 2013-08-08 2015-02-19 独立行政法人日本原子力研究開発機構 Apparatus and method for recovery of metal ion
CN104600299A (en) * 2015-01-08 2015-05-06 华中科技大学 Negative electrode active material for lithium-ion/sodium-ion battery, negative electrode and battery
CN106374137A (en) * 2016-09-18 2017-02-01 电子科技大学 Organic negative electrode material of potassium ion battery and preparation method of organic negative electrode material
CN106602020A (en) * 2016-12-22 2017-04-26 安泰科技股份有限公司 Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material
CN107732302A (en) * 2017-10-11 2018-02-23 西安交通大学 A kind of nonaqueous electrolytic solution and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015034315A (en) * 2013-08-08 2015-02-19 独立行政法人日本原子力研究開発機構 Apparatus and method for recovery of metal ion
CN104600299A (en) * 2015-01-08 2015-05-06 华中科技大学 Negative electrode active material for lithium-ion/sodium-ion battery, negative electrode and battery
CN106374137A (en) * 2016-09-18 2017-02-01 电子科技大学 Organic negative electrode material of potassium ion battery and preparation method of organic negative electrode material
CN106602020A (en) * 2016-12-22 2017-04-26 安泰科技股份有限公司 Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material
CN107732302A (en) * 2017-10-11 2018-02-23 西安交通大学 A kind of nonaqueous electrolytic solution and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QING ZHANG ET AL: "Boosting the Potassium Storage Performance of Alloy-Based Anode Materials via Electrolyte Salt Chemistry", 《ADVANCED ENERGY MATERIALS》 *
柯霖波: "磷化锗作为锂/钠离子电池负极材料的研究", 《中国优秀硕士学位论文全文数据库工程科技II辑》 *

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Inventor after: Li Wenwu

Inventor after: Liu Guoping

Inventor after: Li Yanhong

Inventor after: Zhang Wenchao

Inventor before: Li Wenwu

Inventor before: Liu Guoping

Inventor before: Li Yanhong

Inventor before: Guo Zaiping

Inventor before: Zhang Wenchao

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191105