CN108134079A - The application of ferric phosphate and phosphoric acid iron composite material as cathode in Dual-ion cell - Google Patents
The application of ferric phosphate and phosphoric acid iron composite material as cathode in Dual-ion cell Download PDFInfo
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- CN108134079A CN108134079A CN201711449563.9A CN201711449563A CN108134079A CN 108134079 A CN108134079 A CN 108134079A CN 201711449563 A CN201711449563 A CN 201711449563A CN 108134079 A CN108134079 A CN 108134079A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the application of ferric phosphate and phosphoric acid iron composite material as negative material in Dual-ion cell, the phosphoric acid iron composite material includes ferric phosphate dopant material and the covering material of ferric phosphate dopant material or ferric phosphate covering material.The ferric phosphate or phosphoric acid iron composite material are micron order or nanometer materials.The invention further relates to a kind of ferric phosphate and phosphoric acid iron composite material negative electrodes, ferric phosphate and phosphoric acid iron composite material are uniformly mixed with carbon black and binding agent, it is then coated on a current collector, up to the ferric phosphate and phosphoric acid iron composite material negative electrode after vacuum dried, slice.Ferric phosphate and phosphoric acid iron composite material have current potential higher as negative material, and dendrite is not generated during repeated charge, does not also generate SEI films, interface resistance is low, coulombic efficiency is high, high security and it is at low cost many advantages, such as；There is capacity height and good cycle using it as the Dual-ion cell that negative material is prepared.
Description
Technical field
The invention belongs to kalium ion battery fields, and in particular, to ferric phosphate and phosphoric acid iron composite material exist as cathode
Application in Dual-ion cell.
Background technology
In recent years, energy crisis getting worse, the demand to novel energy are increasingly urgent.Research and develop novel alternative energy
Source and energy-saving and emission-reduction have important development strategic importance.And lithium ion battery as a kind of environmentally protective new energy increasingly by
To the attention of people.High power capacity, long-life, safe new type lithium ion battery become the target that people pursue.Lithium ion
As representative secondary cell, it refers to using lithium ion inlaid scheme as the total of the battery of positive and negative electrode material battery
Claim.Its operation principle is, in battery charging process, lithium ion is deviate from from anode, moves in cathode and embedded electrode material.
Positive electrode is the important component of lithium ion battery, mainly includes cobalt acid lithium, LiMn2O4, LiFePO4, nickel ternary at present
Cobalt manganese, nickel cobalt aluminum material.But in recent years with lithium ion battery, particularly power vehicle and the quick demand in energy storage field,
The price of lithium ion cell positive raw material, particularly metal material is caused quickly to go up.And since positive electrode is transition
The lattice material of metal composition, there are larger hidden dangers for safety, and in overcharge, the lattice for easily leading to positive electrode occurs to break
It is bad, amount of heat is discharged, and oxidation can be generated, the generation of self-catalysis thermal response.There is relatively low electronic conduction additionally, due to anode
Rate needs that a large amount of conductive agent carbon black is coordinated to promote the conductivity of material.Therefore, positive electrode of the prior art is great
Constrain the promotion of lithium ion battery energy density.
Dual-ion cell is a kind of new mentality of designing proposed in recent years, it is based on double ion（Anion, sun from
Son）It can be embedded into electrode positive and negative pole material simultaneously, carry out the mode of energy storage.With the charge-discharge principle of lithium ion battery not
Together, Dual-ion cell is in charging process, anion insertion graphite anode, the embedded cathode of cation, the negative and positive in discharge process
Ion is returned to from positive and negative anodes abjection in electrolyte.The shortcomings that this design overcomes single ion battery respectively.For example, in anode stone
Ink material has layer structure, and the new secondary battery for making anode in embedding graphite carbon-coating is inserted with anion, such as double carbon batteries.Relatively
For lithium ion battery, Dual-ion cell have positive electrode is easy to get, stable structure, reversible potential are high, it is environmental-friendly, can answer
The advantages that for extensive energy storage, becomes the focus of Recent study.
Dual-ion cell can practical application and its capacity and cycle performance it is closely bound up.Since the capacity of anode is with charging
The raising of current potential and increase, the system as anion inserts embedding graphite, highest it is reversible insert embedding current potential in 5.4 V or so.So
And in charging process when voltage reaches 5V or so, common Dual-ion cell organic solvent can be by oxygenolysis, therefore capacity
It cannot be improved with cycle performance.Organic solvent with wide electrochemical window, high anode stability, high-k becomes in recent years
To study the hot spot solvent that anion under high voltage inserts embedding graphite electrode.The mainly fluoro ethylene carbonate of most study at present
Ester, but the embedding capacity highest of inserting of 1mol/L lithium hexafluoro phosphates only has 100 mAh/g, and be recycled to 200 in newest report
Capacity starts to be remarkably decreased during circle.Therefore, the anion for electrolyte being formed based on organic solvent and lithium salts inserts embedding graphite electrode
Capacity and cycle performance are not effectively improved.
It is a kind of one of ideal measure by the voltage window for reducing full battery system, and reaches in cathode voltage
While 5.5 V, the negative material for selecting the stable structure of higher voltage platform is important and significant work.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide ferric phosphate and phosphoric acid iron composite material as cathode
Application of the material in Dual-ion cell.Ferric phosphate provided by the invention and phosphoric acid iron composite material are prepared as negative material
Obtained Dual-ion cell has the advantages that capacity height and good cycle.
Another object of the present invention is to provide a kind of ferric phosphate and phosphoric acid iron composite material negative electrode.
Another object of the present invention is to provide a kind of Dual-ion cell.
To achieve the above object, the present invention adopts the following technical scheme that：
The application of ferric phosphate and phosphoric acid iron composite material as negative material in Dual-ion cell, the phosphoric acid iron composite material
Including ferric phosphate dopant material（MFePO4）And the covering material of ferric phosphate dopant material or ferric phosphate covering material.
Wherein, M Li, Na, K, Al and other metals or nonmetalloid.
The present invention is selected with the ferric phosphate compared with high platform current potential or phosphoric acid iron composite material as the negative of Dual-ion cell
Pole material, the increase of cathode plateau potential reduce the voltage window of all systems, improve the stability of electrolyte.So that it prepares
The cycle performance of obtained Dual-ion cell and safety greatly improve.
Preferably, the ferric phosphate or ferric phosphate dopant material are micron order or nanometer materials.
Preferably, the structure of the ferric phosphate and ferric phosphate dopant material is the porous spherical of micro-nano structure.This stabilization
Structure can increase substantially the invertibity of lithium ion transport, realize macrocyclic performance.
Preferably, the ferric phosphate dopant material is one in LiFePO4, phosphoric acid ferrisodium, ferric phosphate aluminium or phosphoric acid ferripotassium
Kind is several.
Preferably, ferric phosphate provided by the invention can be prepared by following several method：
（1）Ferric phosphate is directly prepared by chemical synthesis process, is obtained by solid-phase synthesis, FeCO3(NH4)3PO4600
Calcining 6h under environment is spent to prepare.FePO is formd in preparation process4Material.It is obtained by above-mentioned calcination temperature and calcination time
Micro-nano structure, stable structure is environmental-friendly, and discharge platform is low, can large-scale application.
（2）Pass through LiFePO4Electrochemical pre-treatment is carried out, above-mentioned material is prepared into battery, MFePO4As anode one
Side, and charging is implemented to the battery of making, in charging process, lithium ion is deviate from from LiFePO 4 material, obtains ferric phosphate
Material, and have a small amount of lithium metal and be entrained in material internal.
（3）Pass through LiFePO4Chemical method pretreatment is carried out, above-mentioned material is dispersed in acetonitrile dissolving, is added in excessive
NOBF45 h of deoxidation.The impurity that removal is not necessarily to, obtains ferric phosphate（FePO4）, and have a small amount of lithium metal of doping in material
It is entrained in material internal.
Commercial product can also be selected from for ferric phosphate, LiFePO4, phosphoric acid ferrisodium, phosphoric acid ferripotassium material.
The present invention protects a kind of ferric phosphate and phosphoric acid iron composite material negative electrode simultaneously, and ferric phosphate and ferric phosphate is compound
Material is uniformly mixed with carbon black and binding agent, is then coated on a current collector, up to the ferric phosphate after vacuum dried, slice
And phosphoric acid iron composite material negative electrode.
The present invention also protects a kind of Dual-ion cell, is cathode by above-mentioned ferric phosphate and phosphoric acid iron composite material negative electrode
Electrode.The Dual-ion cell further includes graphite anode, diaphragm and electrolyte between anode and cathode.
Preferably, the electrolyte of the Dual-ion cell includes organic solvent, electrolyte and additive.
Preferably, the electrolyte is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic acid two
One or more of methyl esters or diethyl carbonate；The electrolyte is lithium hexafluoro phosphate, LiBF4, difluoro oxalate boric acid
Lithium, dioxalic acid lithium borate, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, sodium hexafluoro phosphate, sodium tetrafluoroborate, two
One or more of fluorine oxalic acid Boratex, dioxalic acid Boratex, double trifluoromethanesulfonimide sodium or double fluorine sulfimide sodium.
Preferably, the molar concentration of electrolyte is 0.5~5 mol/L in the electrolyte.
Preferably, the positive electrode for just extremely including graphite, carbon black of the Dual-ion cell.Graphite type material has layer
Shape carbon-coating structure can carry out reversible insertion or abjection anion, store energy.In addition, graphite is just having electrode material
Material is easy to get, stable structure, reversible potential are high, environmental-friendly and the advantages of can be applied to extensive energy storage.
Diaphragm of the present invention is material well known to those skilled in the art, and it is not specifically limited to this by the present invention, preferably
For glass fibre.
Preferably, the organic solvent includes linear carbonate；The linear carbonate is preferably dimethyl carbonate, carbonic acid
One or more of diethylester and methyl ethyl carbonate, more preferably methyl ethyl carbonate.The present invention is to the linear carbonate
Source is not particularly limited, and using the linear carbonate of mentioned kind well known to those skilled in the art, can be purchased by market
Buy acquisition.
Using linear carbonate as the organic solvent of electrolyte, with excellent inoxidizability, electricity can be significantly improved
The oxidation resistance of liquid is solved, and linear carbonate viscosity is low, can increase the solubility of electrolyte, significantly improves the electricity of electrolyte
The multiplying power property of conductance and Dual-ion cell, so as to be effectively improved the capacity of Dual-ion cell and cycle performance.
Compared with prior art, the present invention has the advantages that：
Ferric phosphate and phosphoric acid iron composite material have current potential higher as negative material, and branch is not generated during repeated charge
Crystalline substance does not generate SEI films yet, interface resistance is low, coulombic efficiency is high, high security and it is at low cost many advantages, such as.The present invention with
Ferric phosphate and phosphoric acid iron composite material are high and good cycle with capacity for the Dual-ion cell that negative material is prepared
Advantage.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
The half-cell charging and discharging curve of ferric phosphate cathode is prepared in Fig. 1 embodiments 1；
The XRD curves for the ferric phosphate negative material that Fig. 2 embodiments 1 are prepared；
The half-cell charging and discharging curve for the graphite anode that Fig. 3 embodiments 1 are prepared；
The charging and discharging curve figure of sodium base Dual-ion cell prepared by Fig. 4 embodiments 2；
The cycle-index figure of sodium base Dual-ion cell prepared by Fig. 5 embodiments 2；
The pattern SEM figures for the ferric phosphate that Fig. 6 embodiments 2 are prepared；
Ferric phosphate after the embedding sodium of ferric phosphate that Fig. 7 embodiments 2 are prepared receive SEM figure.
Specific embodiment
Further illustrated the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
The preparation of 1 ferric phosphate negative electrode of embodiment and lithium base Dual-ion cell
（1）The preparation of ferric phosphate negative electrode
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, obtain ferric phosphate negative electrode and used for Dual-ion cell.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of lithium base Dual-ion cell
Graphite anode and ferric phosphate negative electrode are assembled, and isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolysis
Liquid is formed for solvent and two part of electrolyte, ethylene carbonate (EC)：Methyl ethyl carbonate (EMC)=3：7, electrolyte 2mol
Lithium hexafluoro phosphate (LiPF6).Dual-ion cell is sealed to, in this Dual-ion cell, is inserted using lithium ion as cathode embedding
Cation.Battery charging and discharging voltage range is 1.2~4.2 V.Charging and discharging currents density is 50~500 mA/g.
Fig. 1 is the half-cell charging and discharging curve that ferric phosphate cathode is prepared in the present embodiment；Fig. 3 is prepared for the present embodiment
The half-cell charging and discharging curve of obtained graphite anode.
Fig. 2 is the XRD curves of ferric phosphate negative material that the present embodiment is prepared.
The preparation of 2 ferric phosphate negative electrode of embodiment and sodium base Dual-ion cell
（1）The preparation of ferric phosphate negative electrode
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, obtain ferric phosphate negative electrode and used for Dual-ion cell.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of sodium base Dual-ion cell
Graphite anode and ferric phosphate negative electrode are assembled, and isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolysis
Liquid is formed for solvent and two part of electrolyte, propene carbonate（PC）：Methyl ethyl carbonate (EMC)=3：7, electrolyte is
1.5mol sodium hexafluoro phosphates (NaPF6).Dual-ion cell is sealed to, in this Dual-ion cell, using sodium ion as negative
Extremely insert embedding cation.Battery charging and discharging voltage range is 1.2~4.2 V.Charging and discharging currents density is 50~500 mA/g.
Fig. 4 and Fig. 5 is respectively the charging and discharging curve figure for the sodium base Dual-ion cell that the present embodiment is prepared and cycle time
Number figure.In Fig. 4, Dual-ion cell can obtain the specific capacity of 120 mAh/g, can reverse efficiency close to 100%, other cycle performance
Preferably, 250 cycles are undergone, capacity retention ratio is higher than 92%（Fig. 5）.
Fig. 6 is the pattern SEM figures for the ferric phosphate that the present embodiment is prepared；Fig. 7 is the phosphoric acid that the present embodiment is prepared
Ferric phosphate after the embedding sodium of iron receive SEM figure.
The preparation of 3 ferric phosphate negative electrode of embodiment and potassium base Dual-ion cell
（1）The preparation of ferric phosphate negative electrode
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, obtain ferric phosphate negative electrode and used for Dual-ion cell.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of potassium base Dual-ion cell
Graphite anode and ferric phosphate negative electrode are assembled, and isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolysis
Liquid is formed for solvent and two part of electrolyte, propene carbonate（PC）：Methyl ethyl carbonate (EMC)=3：7, electrolyte is
1.5mol Potassium Hexafluorophosphates (NaPF6).Dual-ion cell is sealed to, in this Dual-ion cell, using potassium ion as negative
Extremely insert embedding cation.Battery charging and discharging voltage range is 1.2~4.2 V.Charging and discharging currents density is 50~500 mA/g.
The preparation of 4 ferric phosphate negative electrode of embodiment and lithium base Dual-ion cell
（1）The preparation of ferric phosphate negative electrode
According to LiFePO4（LixFePO4, x≤1）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing is uniformly mixed
Afterwards, coating on a current collector, after vacuum dried, slice, obtains iron phosphate lithium electrode.By iron phosphate lithium electrode and lithium electrode group
Half-cell is dressed up, isolation film is tri- layers of isolation films of PP/PE/PP, and adds in bath composition.In order to carry out pre- de- lithium to battery,
Need LiFePO4 being assembled into half-cell as anode and carry out de- lithium storage lithium, the structure of this battery for LiFePO4 just
Pole-lithium an- ode.It charges the battery, electric current is 0.1 C, and battery is charged to 4 V.In charging process, lithium is gradual
Abjection, is changed into ferric phosphate（FePO4）Or LiFePO4（LixFePO4, x≤0.2）Material, lithium content are less than 0.2.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of lithium base Dual-ion cell
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, ferric phosphate negative electrode is obtained.Graphite anode and ferric phosphate negative electrode are assembled, and
Isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolyte is formed for solvent and two part of electrolyte, propene carbonate
（PC）：Methyl ethyl carbonate (EMC)=3：7, electrolyte is 1.5mol lithium hexafluoro phosphates (LiPF6).It is sealed to double ion electricity
In this Dual-ion cell, embedding cation is inserted using lithium ion as cathode for pond.Battery charging and discharging voltage range is 1.2~4.2
V.Charging and discharging currents density is 50~500 mA/g.
The preparation of 5 ferric phosphate negative electrode of embodiment and sodium base Dual-ion cell
（1）Ferric phosphate negative material is prepared from phosphoric acid ferrisodium electrochemical method abjection sodium element
By phosphoric acid ferrisodium（NaFePO4）It is dispersed in acetonitrile dissolving, adds in excessive NOBF45 h of deoxidation.Removal is not necessarily to
Impurity, obtain ferric phosphate（FePO4）Or phosphoric acid ferrisodium（NaxFePO4, x≤0.2）Material, sodium content are less than 0.2.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of sodium base Dual-ion cell
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, ferric phosphate negative electrode is obtained.Graphite anode and ferric phosphate negative electrode are assembled, and
Isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolyte is formed for solvent and two part of electrolyte, propene carbonate
（PC）：Methyl ethyl carbonate (EMC)=3：7, electrolyte is 1.5mol sodium hexafluoro phosphates (NaPF6).It is sealed to double ion electricity
In this Dual-ion cell, embedding cation is inserted using sodium ion as cathode for pond.Battery charging and discharging voltage range is 1.2~4.2
V.Charging and discharging currents density is 50~500 mA/g.
The preparation of 6 ferric phosphate negative electrode of embodiment and potassium base Dual-ion cell
（1）Ferric phosphate negative material is prepared from phosphoric acid ferripotassium electrochemical method abjection potassium element
By phosphoric acid ferripotassium（KFePO4）It is dispersed in acetonitrile dissolving, adds in excessive NOBF45 h of deoxidation.Removal is not necessarily to
Impurity, obtain ferric phosphate（FePO4）Or phosphoric acid ferripotassium（KxFePO4, x≤0.2）Material, potassium content are less than 0.2.
（2）The preparation of graphite anode electrode
According to graphite：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coating on a current collector, pass through
After vacuum drying, slice, obtain graphite anode electrode and used for Dual-ion cell.
（3）The preparation of potassium base Dual-ion cell
According to ferric phosphate（FePO4）：Carbon black：Binding agent=8:1:1 ratio（Mass ratio）Mixing, after mixing, coated in collection
On fluid, after vacuum dried, slice, ferric phosphate negative electrode is obtained.Graphite anode and ferric phosphate negative electrode are assembled, and
Isolation film glass fibre is sandwiched in centre, adds in electrolyte, electrolyte is formed for solvent and two part of electrolyte, propene carbonate
（PC）：Methyl ethyl carbonate (EMC)=3：7, electrolyte is 1.5mol Potassium Hexafluorophosphates (KPF6).It is sealed to Dual-ion cell,
In this Dual-ion cell, embedding cation is inserted using potassium ion as cathode.Battery charging and discharging voltage range is 1.2~4.2 V.
Charging and discharging currents density is 50~500 mA/g.
The performance of Dual-ion cell that the various embodiments described above are prepared is tested, test method is as follows, charge and discharge
Electric current is 1/3C, and test result see the table below 1.
The performance test of Dual-ion cell that 1 each embodiment of table is prepared
。
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide range caused.
Claims (10)
1. the application of ferric phosphate and phosphoric acid iron composite material as negative material in Dual-ion cell, which is characterized in that described
Phosphoric acid iron composite material includes ferric phosphate dopant material and the covering material of ferric phosphate dopant material or ferric phosphate covering material.
2. apply according to claim 1, which is characterized in that the ferric phosphate or phosphoric acid iron composite material for micron order or are received
Meter level material.
3. apply according to claim 2, which is characterized in that the structure of the ferric phosphate and ferric phosphate dopant material is micro-nano
The porous spherical of structure.
4. apply according to claim 1, which is characterized in that the ferric phosphate dopant material for LiFePO4, phosphoric acid ferrisodium,
One or more of ferric phosphate aluminium or phosphoric acid ferripotassium.
5. a kind of ferric phosphate and phosphoric acid iron composite material negative electrode, which is characterized in that by ferric phosphate and phosphoric acid iron composite material
It is uniformly mixed, is then coated on a current collector with carbon black and binding agent, up to the ferric phosphate and phosphorus after vacuum dried, slice
Sour iron composite material negative electrode.
6. a kind of Dual-ion cell, which is characterized in that select ferric phosphate and phosphoric acid iron composite material negative electricity described in claim 5
Extremely negative electrode.
7. Dual-ion cell according to claim 6, which is characterized in that the electrolyte of the Dual-ion cell includes organic molten
Agent, electrolyte and additive.
8. Dual-ion cell according to claim 7, which is characterized in that the electrolyte is ethylene carbonate, propylene carbonate
One or more of fat, methyl ethyl carbonate, dimethyl carbonate, dimethyl carbonate or diethyl carbonate；The electrolyte is six
Lithium fluophosphate, LiBF4, difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate, double trifluoromethanesulfonimide lithiums, double fluorine sulphonyl
Imine lithium, sodium hexafluoro phosphate, sodium tetrafluoroborate, difluoro oxalate Boratex, dioxalic acid Boratex, double trifluoromethanesulfonimide sodium
Or one or more of double fluorine sulfimide sodium.
9. Dual-ion cell according to claim 7, which is characterized in that the molar concentration of electrolyte is in the electrolyte
0.5~5 mol/L.
10. Dual-ion cell according to claim 6, which is characterized in that the Dual-ion cell just extremely include graphite,
The positive electrode of carbon black.
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| CN201711449563.9A CN108134079A (en) | 2017-12-27 | 2017-12-27 | The application of ferric phosphate and phosphoric acid iron composite material as cathode in Dual-ion cell |
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| CN110600736A (en) * | 2019-08-22 | 2019-12-20 | 深圳先进技术研究院 | Non-metal ion secondary battery and preparation method thereof |
| CN112853375A (en) * | 2021-01-18 | 2021-05-28 | 复旦大学 | Method for co-producing caustic soda and ferric orthophosphate |
| CN113707943A (en) * | 2021-08-25 | 2021-11-26 | 中国科学院长春应用化学研究所 | Electrolyte and double-ion battery |
| CN113972364A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Preparation method of layered carbon-doped sodium iron phosphate cathode material |
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| CN113707943A (en) * | 2021-08-25 | 2021-11-26 | 中国科学院长春应用化学研究所 | Electrolyte and double-ion battery |
| CN113972364A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Preparation method of layered carbon-doped sodium iron phosphate cathode material |
| CN114335693A (en) * | 2021-12-28 | 2022-04-12 | 盐城工学院 | High-safety iron-based phosphate sodium ion full cell and preparation method thereof |
| CN114335693B (en) * | 2021-12-28 | 2023-09-12 | 盐城工学院 | High-safety iron-based phosphate sodium ion full battery and preparation method thereof |
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