CN107431204A - Sodium ion and kalium ion battery anode - Google Patents

Sodium ion and kalium ion battery anode Download PDF

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Publication number
CN107431204A
CN107431204A CN201680015368.2A CN201680015368A CN107431204A CN 107431204 A CN107431204 A CN 107431204A CN 201680015368 A CN201680015368 A CN 201680015368A CN 107431204 A CN107431204 A CN 107431204A
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anode
carbon
metal
carbon composite
polymer
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肖恩.韦尔
鲁宇浩
汪龙
西岛主明
李宗沾
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Sharp Corp
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Sharp Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Mixed for manufacturing the first method of the anode for sodium ion and kalium ion battery, including by the conductive carbon material with low surface area, hard carbon material and adhesive material.It is consequently formed carbon composite and is coated onto in conductive substrates.Mixed for manufacturing the second method of the anode for sodium ion and kalium ion battery, including by metal-containing material, hard carbon material and adhesive material.It is consequently formed carbon composite and is coated onto in conductive substrates.For manufacturing the third method of the anode for sodium ion and kalium ion battery, there is provided there is the hard carbon material of pyrolyzed-polymer coating, the hard carbon material is mixed with adhesive material to form carbon composite, and is coated onto on conductive base.Present invention also offers the Anode and battery manufactured by the above method.

Description

Sodium ion and kalium ion battery anode
Technical field
The present invention relates to electrochemical cell, more specifically to the carbon anode for sodium ion and kalium ion battery.
Background technology
Although sodium (Na) metal is sodium-ion battery (NIB) ideal chose, its application in commercial battery by The limitation of safety problem, such as flammable, dendritic growth and low melting point during charge/discharge.As metal Na substitute, Carbon anode has become NIB attractive candidate.
Generally, carbonaceous material has three allotropes, is diamond, graphite and buckminsterfullerence [NPL respectively 1].In lithium ion battery (LIB) application, graphite and its ordered form are conventional and practical anode materials.Graphite has Typical layer structure, lithium ion (Li+) can reversible insertion/deintercalation therefrom.Due to sodium ion (Na+) and potassium ion (K+) Size relative to lithium ion (Li+) larger, the small graphite of interfloor distance is not suitable for the insertion of sodium/potassium, therefore shows low Capacity [NPL 2].Under some experiment conditions, amorphous carbonaceous materials can be produced.According to crystallinity, these materials can enter One step is classified as " soft carbon " (SC, graphitizable carbon) or " hard carbon " (HC, non-graphitized carbon).In fact, amorphous carbonaceous Material has shown the superperformance of the anode as NIBs.Carbon black, a type of soft carbon, is reported as in NIBs Anode material, wherein sodium, which are presented, can reversibly be embedded in its amorphous and non-porous structure [NPL 3], meanwhile, in 0V-2V (vs.Na/Na+) between its reversible capacity be~200 MAhs/g (mAh/g).Because carbon black has intimate negligible hole Gap rate, it is believed that its larger external surface area can promote the reaction with sodium.However, for the larger irreversible of carbon black anode For capacity, its larger surface area is also unfavorable.
In order to overcome the low capacity of soft carbon material and low coulombic efficiency, hard carbon is being furtherd investigate as NIB anodes, and And confirm its reversible capacity more than 250mAh/g [NPL4,5].The embedding sodium of hard carbon electrode includes two different techniques.In high electricity Press scope (sloped region), Na+Embedded parallel graphene layer.In low voltage range (platform area), Na+In the hole of embedded hard carbon.So And, it is notable that low-voltage platform and Na/Na+Compared to very close 0V, to be applied when the high current for being used for the embedding sodium of HC Added-time, it can enter to be about to the technique that sodium is electroplated onto on hard carbon electrode.Simultaneously as to the high polarization of hard carbon electrode, high current is led Capacity is caused to reduce.Therefore, conductive carbon black is added in HC electrodes, to reduce electrode resistance [NPL 6,7].Certainly, carbon black Can be that hard carbon electrode contributes big irreversible capacity (low coulombic efficiency, CE) in first circle.
For applicant by influence of more several conductive carbonaceous additives to hard carbon electrode performance, it explicitly indicates that CE adds with carbon Add the surface area of agent directly related.More specifically, due to forming solid electrolyte interface (SEI) layer on electrode, conductive carbon The high surface area of additive is related to obvious irreversible capacity.In addition, the different functional groups on these carbonaceous additive surfaces Contribute to the high irreversible capacity of hard carbon electrode and corresponding low CE.
Reference listing
[non-patent literature]
[NPL 1]
Z.Ogumi and M.Inaba, " the electrochemical lithium insertion in carbonaceous material：Telescopiny, surface filming and lithium diffusion (Electrochemical Lithium Intercalation within Carbonaceous Materials: Intercalation Processes, Surface Film Formation, and Lithium Diffusion) ", Japanization Association's circular (Bulletin of the Chemical Society of Japan), 71 (1998) 521-534.
[NPL 2]
M.M.Doeff, Y.Ma, S.J.Visco, and L.C.De Jonghe, " into carbon electrochemical intercalation sodium (Electrochemical Insertion of Sodium into Carbon) ", electrochemistry journal (Journal of the Electrochemical Society), 140 (1993), L169-L170.
[NPL 3]
R.Alcantara, J.M.Jimenez-Mateos, P.Lavela, and J.Tirado, " carbon black：It is a kind of promising Electrode material (Carbon Black for sodium-ion battery:a Promising Electrode Material for Sodium-Ion Batteries) ", electrochemistry communication (Electrochemistry Communications), 3 (2001), 639-642。
[NPL 4]
X.Xia and J.R.Dahn, " Na/ hard carbons and different solvents and reaction Journal of Sex Research (the Study of the of electrolyte Reactivity of Na/Hard Carbon with Different Solvents and Electrolytes) ", electrification Learn journal (Journal of the Electrochemical Society), 159 (2012), A515-A519.
[NPL 5]
S.Kuze,J.-i.Kageura,S.Matsumoto,T.Nakayama,M.Makidera,M.Saka, T.Yamaguchi, T.Yamamoto, and K.Nakane, " development (the Development of a of sodium ion secondary battery Sodium Ion Secondary Battery), SUMITOMO KAGAKU, 2013,1-13.
[NPL 6]
A.Ponrouch, A.R.Goni, and M.R.Palacin, " high power capacity hard carbon anode is used to the addition of free electrolyte Sodium-ion battery (High Capacity Hard Carbon Anodes for Sodium Ion Batteries in Additive Free Electrolyte) ", electrochemistry communication (Electrochemistry Communications), 27 (2013), 85-88.
[NPL 7]
S.Komaba,W.Murata,T.Ishikawa,N.Yabuuchi,T.Ozeki,T.Nakayama,A.Ogata, K.Gotoh, and K.Fujiwara, " be used for hard carbon electrode sodium electrochemical intercalation and solid electrolyte interface and its Na from Application (Electrochemical Na Insertion and Solid Electrolyte Interphase in sub- battery For Hard-Carbon Electrodes and Application to Na-Ion Batteries) ", Premium Features material (Advanced Functional Materials), 21 (2011), 3859-3867.
The content of the invention
Technical problem
If the hard carbon electrode for sodium ion and kalium ion battery can be produced, and it is proved under high-intensity currrent To be favourable with high CE with Large Copacity and in first circle.
Technical scheme
According to an aspect of the present invention, it is a kind of for sodium ion and the hard carbon anode of kalium ion battery, the anode bag Include：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：Hard carbon material；Conductive carbon material with low surface area； Adhesive material；And wherein the carbon composite is defined as the mixture of two or more different materials, wherein at least A kind of material is carbon material.
According to an aspect of the present invention, a kind of side for being used to manufacture the hard carbon anode for sodium ion and kalium ion battery Method, methods described include：
Conductive carbon material with low surface area, hard carbon material and adhesive material are mixed；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein At least one material is carbon material；
By the carbon composite coated in conductive substrates.
According to an aspect of the present invention, it is a kind of to include for sodium ion and the anode of kalium ion battery, the anode：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：Hard carbon material；Metal-containing material；Adhesive material；With And wherein the carbon composite is defined as the mixture of two or more different materials, wherein at least one material is carbon Material.
According to an aspect of the present invention, a kind of method for being used to manufacture the anode for sodium ion and kalium ion battery, Methods described includes：
Metal-containing material, hard carbon material and adhesive material are mixed；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein At least one material is carbon material；
By the carbon composite coated in conductive substrates.
According to an aspect of the present invention, it is a kind of to include for sodium ion and the anode of kalium ion battery, the anode：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：Hard carbon material with pyrolyzed-polymer coating；Adhesive Material；And wherein the carbon composite is defined as the mixture of two or more different materials, wherein at least one material Material is carbon material.
According to an aspect of the present invention, a kind of method for being used to manufacture the anode for sodium ion and kalium ion battery, Methods described includes：
Hard carbon material with pyrolyzed-polymer coating is provided；
The hard carbon material with the pyrolyzed-polymer coating is mixed with adhesive material；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein At least one material is carbon material；
By the carbon composite coated in conductive substrates.
According to an aspect of the present invention, a kind of sodium ion or kalium ion battery, the battery include：
The cyanogen of transition metal six closes metal acid-salt (TMHCM) negative electrode；
Electrolyte；
Anode, including：Conductive substrates；The carbon composite of the conductive substrates is covered, it includes：Hard carbon material；Have The conductive carbon material of low surface area；Adhesive material；The carbon composite is defined as the mixed of two or more different materials Compound, wherein at least one material are carbon materials；
And by anode and the ion permeable membrane of cathode isolation.
According to an aspect of the present invention, a kind of sodium ion or kalium ion battery, the battery include：
The cyanogen of transition metal six closes metal acid-salt (TMHCM) negative electrode；
Electrolyte；
Anode, including：Conductive substrates；The carbon composite of the conductive substrates is covered, the carbon composite includes：Firmly Carbon material；Metal-containing material；Adhesive material；The carbon composite is defined as the mixing of two or more different materials Thing, wherein at least one material are carbon materials；
And by anode and the ion permeable membrane of cathode isolation.
According to an aspect of the present invention, a kind of sodium ion or kalium ion battery, the battery include：
Six cyanogen alloys belong to sour transition metal salt (TMHCM) negative electrode；
Electrolyte；
Anode, it includes：Conductive substrates；The carbon composite of the conductive substrates is covered, including：With pyrolyzed-polymer The hard carbon material of coating；Adhesive material；And the carbon composite is defined as the mixing of two or more different materials Thing, wherein at least one material are carbon materials；
And by anode and the ion permeable membrane of cathode isolation.
The present invention can provide a kind of hard carbon electrode for being prepared for sodium ion or kalium ion battery, and the battery is in height With high CE with Large Copacity and in first circle under intensity currents.
Brief description of the drawings
Fig. 1 describes the schematic diagram of the hard carbon anode for sodium ion and kalium ion battery.
Fig. 2 describes uses 1M NaPF in EC/DEC electrolyte6, in the electricity of 2V to the HC/Na circulated between 0.005V half Pond (1.1mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
Fig. 3 describes uses 1M NaPF in EC/DEC electrolyte6, in the electricity of 2V to the HC/Na circulated between 0.005V half Pond (2.1mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
Fig. 4 describes uses 1M NaPF in EC/DEC electrolyte6, the electricity of the HC/Na that is circulated between 2V and 0.005V half Pond (3.3mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charging.
Fig. 5 describes uses 1M NaClO in EC/DEC electrolyte4, the HC/Na circulated between 2V and 0.005V is partly Battery (1.2mg/cm2HC load) 0.2C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
Fig. 6 illustrates the flow chart of the first method for manufacturing the hard carbon anode for sodium ion and kalium ion battery.
Fig. 7 describes the second plate for sodium ion and kalium ion battery.
Fig. 8 illustrates the flow chart of the second method for manufacturing the hard carbon anode for sodium ion and kalium ion battery.
Fig. 9 A describe the step in the method that pyrolyzed-polymer coating is formed on hard carbon material.
Fig. 9 B describe the step in the method that pyrolyzed-polymer coating is formed on hard carbon material.
Figure 10 describes the third anode for sodium ion and kalium ion battery.
Figure 11 illustrates the flow of the third method for manufacturing the hard carbon anode for sodium ion and kalium ion battery Figure.
Figure 12 is the partial sectional view of sodium ion or kalium ion battery.
Figure 13 is the partial sectional view of the first modification of sodium ion or kalium ion battery.
Figure 14 is the partial sectional view of the second modification of sodium ion or kalium ion battery.
Embodiment
In order to improve coulombic efficiency (CE) purpose, influence of several conductive carbonaceous additives to hard carbon electrode performance is clearly It is determined that reversible capacity and CE are directly related with the surface area of carbon material.More specifically, due to solid electrolyte on hard carbon electrode The formation of interface (SEI) layer, the high surface area of conductive carbonaceous additive are related to obvious irreversible capacity.In addition, these are added The different functional groups of agent also contribute to the high irreversible capacity of hard carbon electrode and low CE.Be disclosed herein that preparation be used for sodium ion and The method of the hard carbon electrode of kalium ion battery, the battery illustrate the Large Copacity under high applied current and had in first circle small Corresponding irreversible capacity high CE.
Focus prepared by hard carbon (HC) electrode is to introduce low surface area and electronic conductive additive to reduce electrode resistance, together Shi Buhui dramatically increases irreversible capacity.The strategy and correlation technique for preparing electrode are not limited to hard carbon (HC) electrode, but can be with Expand to including the various replacement anodes made of the carbonaceous material of graphite and soft carbon material.
It has been disclosed herein that the electrode preparation method of sodium ion and kalium ion battery." activity " material for anode electrode Including carbonaceous material, particularly hard carbon material.Conductive carbon material with small surface area is introduced in HC electrodes to replace big table Area material such as carbon black.Or metal-containing material is also employed as the electronic conductive additive in electrode.Metal-containing material can be with Deposit or coated on HC materials or electrode.Metal-containing material can mix with the HC materials in electrode, or metal-containing material It can be deposited on the surface of HC materials.HC materials can be distributed in polymer, or are effectively coated by polymer, then It is pyrolyzed to provide conductive coating on HC materials.
Therefore, for first method of the manufacture for sodium ion and the hard carbon anode of kalium ion battery, there will be low table Conductive carbon material, hard carbon material and the adhesive material mixing of area.Carbon composite is consequently formed, the carbon composite exists The herein defined as mixture of two or more different materials, wherein at least one material are carbon materials.The carbon is answered Condensation material is coated in conductive substrates.Described adhesive material, for example, being the mixture of polymer or polymer.The conduction Carbon material, which has, is less than 100m2/g(m2/ g) surface area.Described adhesive material is execution " being combined together " electrode material work( Can, and give electrode structure and mechanical integrity.
For manufacturing the second method of the anode for sodium ion and kalium ion battery, by metal-containing material, hard carbon material Material and adhesive material mixing.It is consequently formed carbon composite and is coated onto in conductive substrates.The metal-containing material can With including transition metal, and metal element, metal hydroxides, metal oxide or form of its combination can be used.Separately On the one hand, the metal-containing material excludes that the material of alloy, such as antimony (Sb) or tin (Sn), wherein institute can be formed with sodium and potassium The material that alloy is defined as being made up of two or more metals is stated, or, the thing of one or more metals and nonmetallic composition Matter.
For manufacturing the third method of the anode for sodium ion and kalium ion battery, there is provided have pyrolyzed-polymer to apply The hard carbon material of layer, the hard carbon material are mixed with adhesive material to form carbon composite, and the carbon composite is applied Overlay in conductive substrates.The hard carbon material with pyrolyzed-polymer coating can be by being dispersed in polymer by hard carbon material In material and it is heat-treated and is formed.Therefore, polymer is pyrolyzed, and the polymer that pyrolysis is formed on the hard carbon material applies Layer.
The description of the additional detail of the above method presented below and the anode manufactured using these methods.
Generally, in organic bath, reversible capacity is consumed during first circle to form solid electrolyte circle on anode Face (SEI) layer, which inhibits further electrochemical dissolution.Because the contact between anode and electrolyte is completely covered in SEI layers Face, corresponding irreversible capacity are substantially related to the surface area of whole electrode.For example, Ketjen black (Ketjen black), for example, There are about 1000 square metres of every gram of (m2/ g) surface area, big capacitance loss (low coulombic efficiency) is produced in first circle.For Hard carbon electrode, carbon black are typically used as electronic conductive additive to reduce electrode resistance and polarization.However, for hard carbon electrode, it is first It is inevitable that the coulombic efficiency of circle, which declines, and it can be reduced to less than 60% from more than 90%.As a result, for sodium ion or The HC anodes structure electronic conduction network of kalium ion battery, while keep sizable coulombic efficiency.
Fig. 1 describes the schematic diagram of the hard carbon anode for sodium ion and kalium ion battery.Anode 100 includes conductive substrates 102, it can be metal, such as copper (Cu), the aluminium (CC-Al) of aluminium (Al) or carbon coating.A kind of carbon composite 104 is covered in In the conductive substrates 102.The carbon composite 104 includes hard carbon material 106, has the conductive carbon material of low surface area 108 and adhesive material 110.As it is used herein, carbon composite is defined as the mixing of two or more different materials Thing, wherein at least one material are carbon materials.The conductive carbon material 108, which has, is less than 100m2/g(m2/ g) surface area.Institute State the mixture that adhesive material 110 is typically polymer or polymer.
Method 1：Low surface area carbonaceous material is as electronic conductive additive
It is above-mentioned observation indicate that, the high surface area of conductive carbon material cause HC anode first circles high irreversible capacity and compared with Low coulombic efficiency.In order to avoid this problem, the conductive carbon material with low surface area is employed as additive for electrode preparation HC electrodes.The surface area of the conductive carbon material can be 0<10m2/ g, 0<20m2/ g, 0<30m2/ g, 0<40m2/ g, 0<50m2/ G, 0<60m2/ g, 0<70m2/ g, 0<80m2/ g, 0<90m2/ g, or 0<100m2/g.The HC anode materials and conductive carbon material, glue Mixture is mixed to manufacture electrode.Described adhesive example can be polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride/difluoride (PVdF), carboxymethyl cellulose (CMC), sodium carboxymethylcellulose (Na-CMC), styrene-butadiene rubber (SBR), algae Acid, mosanom and combinations thereof, but other adhesive materials can also be used.
This section discusses real as the operation of the high-performance HC electrodes of additive for electrode comprising low surface area conductive carbon material Example.Although HC is the carbonaceous anode materials as exemplary purposes used, suitable substitute such as soft carbon and graphite are also It is similar possible.Using including HC, low surface area conductive carbon (surface area~45m2/ g) and PVdF (KYNAR HSV900) Slurry prepares HC electrodes, and the electrode is by HC (75 weight %), low surface area conductive carbon material (20 weight %) and PVdF (5 weights Measure %) composition.By caused slurry coated on Cu paper tinsels.
Coin battery (HC/Na half-cells) is manufactured to electrode using above-mentioned electrode and sodium (Na) metal, between HC and Na Na between electrode+Permeable membrane, and ethylene carbonate-diethyl carbonate (EC-DEC) of sodium hexafluoro phosphate containing 1M (NaPF 6) As electrolyte.Between 2V and 5mV, by maintain charge-discharge velocity for 50 milliamperes every gram (mA/g) (0.2C, 5 circulation) → 100 (mA/g) (0.4C, 5 circulations) → 125mA/g (0.5C, 10 circulations) → 250mA/g (1C, 10 circulations) → 500mA/ G (2C, 10 circulations) → 1000mA/g (4C, 10 circulations) → 50mA/g (0.2C) is circulated.As in Figure 2-4, use 1M NaPF6(EC-DEC) the charged/discharged curve of the HC/Na half-cell structures of electrolyte, wherein HC electrodes [HC (75 weights Measure %), low surface area conductive carbon material (20 weight %), PVdF (5 weight %)/Cu]) there are 3 kinds of different HC mass loadings (1.1mg/cm2, 2.1mg/cm2And 3.3mg/cm2).As shown in figure 5,1M sodium perchlorates are used in EC-DEC electrolyte (NaClO4) HC/Na half-cell structures charged/discharged curve, wherein [HC (75 weight %), low surface area are conductive for HC electrodes Carbon material (20 weight %), PVdF (5 weight %)/Cu] there is 1.2mg/cm2HC mass loadings.
Fig. 2 describes uses 1M NaPF in EC/DEC electrolyte6, in the electricity of 2V to the HC/Na circulated between 0.005V half Pond (1.1mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
Fig. 3 describes uses 1M NaPF in EC/DEC electrolyte6, in the electricity of 2V to the HC/Na circulated between 0.005V half Pond (2.1mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
Fig. 4 describes uses 1M NaPF in EC/DEC electrolyte6, the electricity of the HC/Na that is circulated between 2V and 0.005V half Pond (3.3mg/cm2HC load) 0.2C, 0.4C, 0.5C, 1C, 2C and 4C rate discharge/charging.
Fig. 5 describes uses 1M NaClO in EC/DEC electrolyte4, the HC/Na circulated between 2V and 0.005V is partly Battery (1.2mg/cm2HC load) 0.2C, 0.5C, 1C, 2C and 4C rate discharge/charge graph.
From Fig. 2-4 as can be seen that for using 1M NaPF6(EC-DEC) HC electrodes [HC (75 weights of electrolyte Measure %), low surface area conductive carbon material (20 weight %), PVdF (5 weight %)/Cu], considerable capacity and corresponding first circle storehouse Human relations efficiency can even maintain medium under higher C- speed (0.5C, 1C).Generally, this may be considered following result (1) Because conductive carbon material causes higher electrode conductivuty as the additive in HC electrodes, and (2) conductive carbon material is low Surface area (~45m2/ g), it will not consume a large amount of capacity during the SEI layers of first circle are formed.Use 1M NaClO4(EC-DEC) Electrolyte, capacity~250mAh/g is realized with 1C speed, it, which is higher than to use, has similar HC mass loadings (1.1-1.2mg/ cm2) 1M NaPF6The capacity (~175mAh/g) that EC-DEC electrolyte is realized.
Fig. 6 illustrates the flow chart of the first method for manufacturing the hard carbon anode for sodium ion and kalium ion battery. Although for the sake of clarity, this method is depicted as a series of numbered step, and numbering might not deciding step Sequentially.It should be appreciated that some steps can be skipped, implement simultaneously, or need not be strict implement according to putting in order. However, generally, methods described follows the numerical order of shown step.This method is since step 600.
Conductive carbon material of step 602 mixing with low surface area, hard carbon material and adhesive material.Step 604 is formed Carbon composite, it is defined herein as the mixture of two or more different materials, and wherein at least one material is carbon materials Material.Step 606 is by the carbon composite coated in conductive substrates.As described above, described adhesive material can be polymerization The mixture of thing or polymer.The conductive carbon material is typically below 100m2/ g surface area.
Method 2：Metal-containing material is as electronic conductive additive
Above-mentioned conductive carbon material can be replaced by metal-containing material.The surface area of metal-containing material can be 0<10m2/ G, 0<20m2/ g, 0<30m2/ g, 0<40m2/ g, 0<50m2/ g, 0<60m2/ g, 0<70m2/ g, 0<80m2/ g, 0<90m2/ g, 0< 100m2/ g, 0<200m2/ g, 0<500m2/ g or 0<1000m2/g.HC materials can be mixed with metal-containing material and adhesive To manufacture electrode.The non-exhaustive list of possible adhesive has been included in upper one section.
In addition, metal-containing material can be coated in the component of the composite on HC materials or as HC materials.The HC Material can be dispersed in the aqueous solution containing soluble metallic salt or metal complex, and metal ion is absorbed into the solution On the surface of hard carbon material.When addition chemical reagent, such as when alkali is to increase pH value of solution, the metal ion conversion on HC is adsorbed Into corresponding metal hydroxides and/or metal oxide, metal-containing material and HC composite are formed.In concrete condition Under, Cu and HC compound can be used as example.HC materials are dispersed in copper (II) ion (Cu2+) the aqueous solution in.It is mixed After conjunction, Cu2+It is absorbed on hard carbon surface.PH value of solution is adjusted using the solution of suitable sodium hydroxide (NaOH) or the like To form HC and Kocide SD/Cu oxide compound.The composite manufactures electrode together with suitable adhesive.With It is appropriate the following batteries of electrode pair are assembled and circulated after, the copper-bearing materials in hard carbon combination electrode are reduced electrochemically For Ni metal, so as to form favourable electronic conduction network in HC electrodes.
Fig. 7 depicts the second plate for sodium ion and kalium ion battery.The anode 700 includes conductive substrates 102 With the carbon composite 702 of covering conductive substrates.The carbon composite 702 includes hard carbon material 106, metal-containing material 704 With adhesive material 110.As the first anode described in Fig. 1, carbon composite is defined herein as two or more The mixture of different materials, wherein at least one material are carbon materials.As described above, described adhesive material can be polymerization The mixture of thing or polymer.
On the one hand, the metal-containing material 704, which has, is less than 100m2/ g surface area.On the other hand, metal-containing material 704 include transition metal.The metal-containing material 704 can take metal element, metal hydroxides, metal oxide or its The form of combination.In addition, in some respects, metal-containing material clearly eliminates the material that alloy can be formed with sodium and potassium, Wherein described alloy set justice is the material being made up of two or more metals, or, one or more metals and nonmetallic composition Material.
Fig. 8 illustrates the flow chart of the second method for manufacturing the anode for sodium ion and kalium ion battery.Institute Method is stated since step 800.Step 802 mixing metal-containing material, hard carbon material and adhesive material.Described adhesive material The typically mixture of polymer or polymer.Step 804 forms carbon composite, and it is defined herein as two or more The mixture of different materials, wherein at least one material are carbon materials.The carbon composite is coated in conductive base by step 806 On bottom.As described above, metal-containing material is typically below 100m2/ g surface area, and transition metal can be included.It is described Metal-containing material can take metal element, metal hydroxides, metal oxide or the form of its combination.In one aspect, The metal-containing material excludes that the material of alloy can be formed with sodium and potassium, and the alloy is as defined above.
Method 3：Use the polymer composites of method for pyrolysis
HC materials are dispersed in polymer to form carbon composite in the method.Then, the carbon compound exists Within the temperature range of 300-2000 DEG C, preferably it is heat-treated in a furnace under inert atmosphere (pyrolysis), so as in HC materials Upper offer pyrolyzed-polymer coating, the HC materials are then mixed with suitable adhesive to prepare electrode.It is pyrolyzed for being formed The suitable polymeric material of polymer coating includes polymer and natural and synthesis polymerization with covalent carbon-carbon bond Thing.
Fig. 9 A and 9B depict on hard carbon material formed pyrolyzed-polymer coating technique the step of.Hard carbon 106 is retouched It is depicted as the solid particle with surface 900.The HC particles 106 are wrapped up by polymer 902 first, then in inert atmosphere conditions Under be heat-treated.Resulting composite 904 has surface 906.Surface area reduce cause SEI layers formed charging/ Small capacity consumption is produced during electric discharge.As a result, the hard carbon material of the pyrolyzed-polymer coating shows high coulomb effect Rate and high power capacity, therefore it is used as the anode in sodium ion and kalium ion battery.
Figure 10 describes the third anode for sodium ion and kalium ion battery.Anode 1000 includes the He of conductive substrates 102 Cover the carbon composite 1002 of the conductive substrates.The carbon composite 1002 includes having pyrolyzed-polymer coating 904 Hard carbon material 106 and adhesive material 110.As described above, the carbon composite is defined herein as two or more The mixture of different materials, wherein at least one material are carbon materials.Similarly, as described above, described adhesive material 110 can be with It is the mixture of polymer or polymer.
Figure 11 illustrates the flow chart of the third method for manufacturing the anode for sodium ion and kalium ion battery.Institute The method of stating starts from step 1100.Step 1102 provides the hard carbon material with pyrolyzed-polymer coating.Step 1104 will have The hard carbon material of pyrolyzed-polymer coating mixes with adhesive material.Generally, described adhesive material is polymer or polymer Mixture.Step 1106 forms carbon composite as described above.Step 1108 is by the carbon composite coated in conduction In substrate.
Following sub-step can be included by providing the hard carbon material with pyrolyzed-polymer coating in step 1102.Step 1102a provides polymeric material.Step 1102b is scattered in the polymeric material by hard carbon material.Step 1102c carries out hot place Reason, such as it is heated to 300-2000 DEG C of temperature.On the one hand, heated in an inert atmosphere.Step 1102d pyrolysis is described poly- Compound.
In a word, all there is hard carbon, and hard carbon is formed with low surface area and high coulomb effect in all three situations The feature of all three schemes of the anode electrode of rate.In addition, the anode electrode with HC materials is advantageous to increase electric conductivity, because There is conductive carbon material (2) metal-containing material of low surface area, or the heat on (3) HC for electronic conduction network by using (1) Depolymerization compound coating is established.Method 1 (HC adds conductive carbon) and method 3 (pyrolyzed-polymer coating) all include conductive carbon material (physics adds or formed pyrolyzed-polymer coating).Contain metal process for method 2, there are two kinds of modifications.In the first situation Under, elemental metal particles are mixed with HC.In finer modification, metal precursor (such as oxide) is deposited to HC table On face.During battery first circle (charge/discharge), (and irreversible) of the metal oxide electrochemical is reduced into element gold Belong to material (on HC surfaces).Subsequently, as the high intrinsic conductance of metal, the metallic particles of formation (is formed in HC electrodes Conductive network) improve the electric conductivity of electrode.
Figure 12 is the partial sectional view of sodium ion or kalium ion battery.Battery 1200 includes the cyanogen alloy of transition metal six category acid Salt (TMHCM) negative electrode 1202 and electrolyte 1204.According to international pure and applied chemistry federation (IUPAC), transition metal quilt It is defined as " its atom has incomplete d subshells, or it can generate the element of the cation with incomplete d subshells ".It is logical Often, transition metal is located at the group of the periodic table of elements the 3rd to 12.Generally, TMHCMs has the A corresponded under discharge conditionxM1nM2m (CN)6.d(H2O chemical formula)；
Wherein " A " is sodium (Na+), potassium (K+) or both combination；
Wherein M1 and M2 is transition metal；
Wherein x is in the range of more than 0 to 4；
Wherein n is in the range of 0 to 2；
Wherein m is in the range of 0 to 2；And
Wherein d is in the range of 1 to 6.
The electrolyte 1204 can be non-aqueous media, polymer, gel or solid material.In non-aqueous (liquid) electrolyte In the case of, electrolyte can include the sodium salt and/or sylvite being dissolved in the mixture of organic solvent or organic solvent.May Sodium salt and the non-exhaustive listing of sylvite include the hexafluorophosphate (NaPF of sodium or potassium6Or KPF6), the perchlorate of sodium or potassium (NaClO4Or KClO4), the tetrafluoroborate (NaBF of sodium or potassium4Or KBF4) and double (trifyl) acyls of sodium or potassium Inferior amine salt (NaTFSI or KTFSI).Some examples of organic solvent include ethylene carbonate (EC), diethyl carbonate (DEC), carbon Dimethyl phthalate (DMC), propene carbonate (PC) and organic ether.
Battery also includes anode 100.It is described in detail in its details such as Fig. 1, is not repeated for simplicity.The anode 100 include conductive substrates 102 and the carbon composite 104 being covered in conductive substrates.The carbon composite 104 includes hard carbon Material 106, there is the conductive carbon material 108 and adhesive material 110 of low surface area.As described above, the carbon composite 104 It is defined as the mixture of two or more different materials, wherein at least one material is carbon material.Herein, the anode 100 It is illustrated to be formed on current-collector 1206, current-collector 1206 may, for example, be conductive carbon material or metal.On the one hand, electric conductivity base Bottom is current-collector.Ion permeable membrane 1208 isolates anode 100 with negative electrode 1202.The ion permeable membrane 1208 charges in battery And sodium and potassium ion is allowed to pass through between anode 100 and negative electrode 1202 during electric discharge.In the situation of liquid (non-aqueous) electrolyte Under, the ion permeable membrane 1208 between anode and negative electrode can be for example from the commercial materials of Celgard purchases Polymer.In polymer, in the case of gel and solid electrolyte, it may not be necessary to extra ion permeable membrane, because these Electrolyte may be used as ion permeable membrane, and they are enough anode and cathode isolation.
Figure 13 is the partial sectional view of the first modification of sodium ion or kalium ion battery.The battery 1300 includes TMHCM Negative electrode 1302 and electrolyte 1304.As depicted in figure 12, the electrolyte 1304 can be non-aqueous media, polymer, coagulate Glue or solid material.As being described in detail in Fig. 7, its details is not repeated for simplicity, and anode 700 includes conductive substrates 102 and covering conductive substrates carbon composite 702.The carbon composite 702 includes hard carbon material 106, metal-containing material 704 and adhesive material 110.Herein, the anode 700 is illustrated to be formed on current-collector 1306, and the current-collector 1306 can To be, for example, conductive carbon material or metal.Ion permeable membrane 1308 isolates anode 700 with negative electrode 1302.
Figure 14 is the partial sectional view of the second modification of sodium ion or kalium ion battery.The battery 1400 includes TMHCM Negative electrode 1402 and electrolyte 1404.The electrolyte 1304 can be non-aqueous media, polymer, gel or solid material.Its is thin Section is not repeated for simplicity as being described in detail in Figure 10.Anode 1000 includes conductive substrates 102 and covering conductive base The carbon composite 1002 at bottom.The carbon composite 1002 includes the He of hard carbon material 106 with pyrolyzed-polymer coating 904 Adhesive material 110.Herein, the anode 1000 is illustrated to be formed on current-collector 1406, and the current-collector 1406 can example Conductive carbon material or metal in this way.Ion permeable membrane 1408 isolates anode 1000 with negative electrode 1402.
The invention provides the method for manufacture sodium ion and kalium ion battery anode.Illustrate certain material and method and step Example to illustrate the present invention.However, the present invention is not limited only to these examples.Those skilled in the art by remember the present invention its Its variant and embodiment.
Following all applications are incorporated herein by reference：(1) synthetic method (the METHOD FOR THE of ferric ferricyanide SYNTHESIS OF IRON HEXACYANOFERRATE), invented by Sean Vail et al., sequence number 14/472,228, August is submitted on the 28th within 2014, attorney docket SLA3396；(2) the cyanogen alloy of the transition metal six category acid containing water-soluble binder Salt electrode (RANSITION METAL HEXACYANOMETALLATE ELECTRODE WITH WATER-SOLUBLE BINDER), by Long Wang et al. inventions, sequence number is submitted on July 24th, 14/340,141,2014, attorney docket SLA3452；(3) the stabilized additive agent electrolyte of transition metal metallocyanide electrode (ELECTROLYTE ADDITIVES FOR TRANSITION METAL CYANOMETALLATE ELECTRODE STABILIZATION), invented by Yuhao Lu et al., Sequence number is submitted on June 30th, 14/320,352,2014, attorney docket SLA3431；(4) for alkali metal-ion battery Hard carbon composite (hard carbon composite for alkali metal-ion batteries), by Xiulei Ji et al. is invented, and sequence number is submitted on June 6th, 62/009,069,2014, attorney docket SLA3416P；(5) metal cyanide gold The synthetic method (METAL CYANOMETALLATE synthesis method) of category, invented by Long Wang et al., sequence Submit in number on June 6th, 62/008,869,2014, attorney docket SLA3430P；(6) containing non-aqueous mixed electrolyte can Charge metal ion battery (RECHARGEABLE METAL-ION BATTERY WITH NON-AQUEOUS HYBRID ION ELECTROLYTE), invented by Long Wang et al., sequence number is submitted on May 7th, 14/271,498,2014, attorney docket SLA3388；(7) reactive separator (the REACTIVE SEPARATOR FOR A METAL-ION of metal ion battery BATTERY), invented by Long Wang et al., sequence number is submitted on March 31st, 14/230,882,2014, attorney docket SLA3370；(8) sodium ion conductor polymer dielectric structure (NASICON-POLYMER ELECTROLYTE STRUCTURE), Invented by Long Wang et al., sequence number is submitted on March 6th, 14/198,755,2014, attorney docket SLA3367；(9) it is pre- Load battery (the BATTERY WITH an anode preloaded with consumable of the anode of easy consumption metal Metals), invented by Yuhao Lu et al., sequence number is submitted on March 6th, 14/198,702,2014, attorney docket SLA3364；(10) galvanic anode (BATTERY ANODE WITH PRELOADED METALS) of preloaded metal, by Long Wang et al. is invented, and sequence number is submitted on March 6th, 14/198,663,2014, attorney docket SLA3363；(11) containing pyrolysis The metal battery electrode (METAL BATTERY ELECTRODE WITH PYROLYZED COATING) of coating, by Yuhao Lu Et al. invention, sequence number 14/193,782,2014 year submits for 28 days 2 months, attorney docket SLA3353；(12) containing shielding knot The cyanogen of metal six of structure closes metal acid-salt electrode (METAL HEXACYANOMETALLATE ELECTRODE WITH SHIELD STRUCTURE), invented by Yuhao Lu et al., sequence number 14/193,501,2014 year is submitted for 28 days 2 months, attorney docket SLA3352；(13) cyano group metallic cathode battery and manufacture method (Cyanometallate Cathode Battery and Method for Fabrication), to be invented by Yuhao Lu et al., sequence number 14/174,171,2014 year is submitted for 6 days 2 months, Attorney docket SLA3351；(14) sodium ion (II)-hexacyanoferrate (II) battery electrode and synthetic method (SODIUM IRON (II)-HEXACYANOFERRATE (II) BATTERY ELECTRODE AND SYNTHESIS METHOD), Yuhao Lu Et al. invention, sequence number submits on October 30th, 14/067,038,2013, attorney docket SLA3315；(15) transition metal six Cyanogen closes metal acid-salt conducting polymer composite material (TRANSITION Metal HexacyanoMETALLATE-CONDUCTIVE POLYMER COMPOSITE), invented by Sean Vail et al., sequence number is submitted on October 22nd, 14/059,599,2013, generation Manage people's Reference Number SLA3336；(16) metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode (Metal-Doped Transition Metal Hexacyanoferrate (TMHCF) Battery Electrode), by human hairs such as Yuhao Lu Bright, sequence number is submitted on June 1st, 13/907,892,2013, attorney docket SLA3287；(17) by ferrocyanide or iron cyanogen Hexacyanoferrate battery electrode (the HEXACYANOFERRATE BATTERY ELECTRODE MODIFIED of compound modification WITH FERROCYANIDES OR FERRICYANIDES), invented by Yuhao Lu et al., sequence number 13/897,492,2013 On May 20, in submits, attorney docket SLA3286；(18) shielded transition metal hexacyanoferrate battery electrode (PROTECTED TRANSITION METAL HEXACYANOFERRATE BATTERY ELECTRODE), by Yuhao Lu etc. People is invented, and sequence number is submitted on April 29th, 13/872,673,2013, attorney docket SLA3285；(19) there is single platform to fill Transition metal hexacyanoferrate cell cathode (the TRANSITION METAL HEXACYANOFERRATE of electricity/discharge curve BATTERY CATHODE WITH SINGLE PLATEAU CHARGE/DISCHARGE CURVE), by human hairs such as Yuhao Lu Bright, sequence number is submitted on January 29th, 13/752,930,2013, attorney docket SLA3265；(20) it is cloudy containing six cyanogen alloys category Pole, super capacitor (the SUPERCAPACITOR WITH HEXACYANOMETALLATE of active carbon anode and aqueous electrolyte CATHODE, ACTIVATED CARBON ANODE, AND AQUEOUS ELECTROLYTE), invented by Yuhao Lu et al., sequence Row number 13/603,322, September is submitted on the 4th within 2012, attorney docket SLA3212；(21) six cyanogen alloys of electrochemical applications Belong to improvement (the IMPROVEMENT OF ELECTRON TRANSPORT IN of the electric transmission in electrode HEXACYANOMETALLATE ELECTRODE FOR ELECTROCHEMICAL APPLICATIONS), by Yuhao Lu et al. Invention, sequence number is submitted on June 14th, 13/523,694,2012, attorney docket SLA3152；(22) six cyanogen alloys are contained Belong to alkali and alkaline earth ion battery (the ALKALI AND ALKALINE-EARTH ION BATTERIES of negative electrode and non-metallic anode WITH HEXACYANOMETALLATE CATHODE AND NON-METAL ANODE), invented by Yuhao Lu et al., sequence Submit in number on April 17th, 13/449,195,2012, attorney docket SLA3151；(23) metal of metal electrode is closed containing six cyanogen Electrode forming method (the Electrode Forming Process for Metal-Ion Battery with of ion battery Hexacyanometallate Electrode), invented by Yuhao Lu et al., sequence number March 28 in 13/432,993,2012 Day submits, attorney docket SLA3146.

Claims (28)

1. a kind of include for sodium ion and the hard carbon anode of kalium ion battery, the anode：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material；
Conductive carbon material with low surface area；
Adhesive material；And
Wherein, the carbon composite is defined as the mixture of two or more different materials, wherein
At least one material is carbon material.
2. anode as claimed in claim 1, wherein conductive carbon material, which have, is less than 100m2/g(m2/ g) surface area.
3. anode as claimed in claim 1, wherein described adhesive material select free polymer and the mixture group of polymer Into group.
4. a kind of method for being used to manufacture the hard carbon anode for sodium ion and kalium ion battery, methods described include：
Conductive carbon material with low surface area, hard carbon material and adhesive material are mixed；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein at least A kind of material is carbon material；And
By the carbon composite coated in conductive substrates.
5. method as claimed in claim 4, wherein described adhesive material select free polymer and the mixture group of polymer Into group.
6. method as claimed in claim 4, wherein the conductive carbon material, which has, is less than 100m2/g(m2/ g) surface area.
7. a kind of include for sodium ion and the anode of kalium ion battery, the anode：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material；
Metal-containing material；
Adhesive material；And
Wherein, the carbon composite is defined as the mixture of two or more different materials, and wherein at least one material is Carbon material.
8. anode as claimed in claim 7, wherein the metal-containing material, which has, is less than 100m2/g(m2/ g) surface area.
9. anode as claimed in claim 7, wherein the metal-containing material includes transition metal.
10. anode as claimed in claim 7, wherein the metal-containing material includes being selected from by metal element, metal hydroxide The material of the group of thing, metal oxide and combinations thereof composition.
11. anode as claimed in claim 7, wherein the metal-containing material excludes that the material of alloy can be formed with sodium and potassium Material, wherein the alloy is defined as the material being made up of two or more metals, or, one or more metals with it is nonmetallic The material of composition.
12. anode as claimed in claim 7, wherein described adhesive material select free polymer or the mixture group of polymer Into group.
13. a kind of method for being used to manufacture the anode for sodium ion and kalium ion battery, methods described include：
Metal-containing material, hard carbon material and adhesive material are mixed；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein at least A kind of material is carbon material；
By the carbon composite coated in conductive substrates.
14. method as claimed in claim 13, wherein metal-containing material, which have, is less than 100m2/g(m2/ g) surface area.
15. method as claimed in claim 13, wherein metal-containing material include transition metal.
16. method as claimed in claim 13, wherein the metal-containing material includes being selected from by metal element, metal hydroxide The material of the group of thing, metal oxide and combinations thereof composition.
17. method as claimed in claim 13, wherein the metal-containing material excludes that the material of alloy can be formed with sodium and potassium Material, wherein the alloy is defined as the material being made up of two or more metals, or, one or more metals with it is nonmetallic The material of composition.
18. method as claimed in claim 13, wherein described adhesive material select the mixture of free polymer or polymer The group of composition.
19. a kind of include for sodium ion and the anode of kalium ion battery, the anode：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material with pyrolyzed-polymer coating；
Adhesive material；And
Wherein, the carbon composite is defined as the mixture of two or more different materials, and wherein at least one material is Carbon material.
20. anode as claimed in claim 19, wherein described adhesive material select the mixture of free polymer or polymer The group of composition.
21. a kind of method for being used to manufacture the anode for sodium ion and kalium ion battery, methods described include：
Hard carbon material with pyrolyzed-polymer coating is provided；
The hard carbon material with the pyrolyzed-polymer coating is mixed with adhesive material；
Carbon composite is formed, the carbon composite is defined as the mixture of two or more different materials, wherein at least A kind of material is carbon material；
By the carbon composite coated in conductive substrates.
22. method as claimed in claim 21, wherein described adhesive material select the mixture of free polymer or polymer The group of composition.
23. method as claimed in claim 21, wherein the hard carbon material with pyrolyzed-polymer coating that provides includes：
Polymeric material is provided；
The hard carbon material is distributed in the polymeric material；
It is heat-treated；With,
It is pyrolyzed the polymer.
24. method as claimed in claim 23, wherein described carry out scope of the heat treatment including being heated at 300-2000 DEG C Interior temperature.
25. method as claimed in claim 23, wherein described carry out heat treatment including being heated in an inert atmosphere.
26. a kind of sodium ion or kalium ion battery, the battery includes：
The cyanogen of transition metal six closes metal acid-salt (TMHCM) negative electrode；
Electrolyte；
Anode, including：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material；
Conductive carbon material with low surface area；
Adhesive material；
Wherein, the carbon composite is defined as the mixture of two or more different materials, and wherein at least one material is Carbon material；
And by anode and the ion permeable membrane of cathode isolation.
27. a kind of sodium ion or kalium ion battery, the battery includes：
The cyanogen of transition metal six closes metal acid-salt (TMHCM) negative electrode；
Electrolyte；
Anode, including：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material；
Metal-containing material；
Adhesive material；
Wherein, the carbon composite is defined as the mixture of two or more different materials, and wherein at least one material is Carbon material；
And by anode and the ion permeable membrane of cathode isolation.
28. a kind of sodium ion or kalium ion battery, the battery includes：
The cyanogen of transition metal six closes metal acid-salt (TMHCM) negative electrode；
Electrolyte；
Anode, including：
Conductive substrates；
The carbon composite of the conductive substrates is covered, including：
Hard carbon material with pyrolyzed-polymer coating；
Adhesive material；
Wherein described carbon composite is defined as the mixture of two or more different materials, and wherein at least one material is Carbon material；
And by anode and the ion permeable membrane of cathode isolation.
CN201680015368.2A 2015-03-13 2016-03-08 Sodium ion and kalium ion battery anode Pending CN107431204A (en)

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US14/656,808 US9742027B2 (en) 2012-03-28 2015-03-13 Anode for sodium-ion and potassium-ion batteries
PCT/JP2016/001264 WO2016147607A1 (en) 2015-03-13 2016-03-08 Anode for sodium-ion and potassium-ion batteries

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