CN106207253B - A kind of aqueous solution lithium ion secondary battery negative pole, electrolyte and battery - Google Patents
A kind of aqueous solution lithium ion secondary battery negative pole, electrolyte and battery Download PDFInfo
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- CN106207253B CN106207253B CN201610821910.5A CN201610821910A CN106207253B CN 106207253 B CN106207253 B CN 106207253B CN 201610821910 A CN201610821910 A CN 201610821910A CN 106207253 B CN106207253 B CN 106207253B
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/255—Tartaric acid
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
- C30B29/56—Tartrates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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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
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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 provides a kind of aqueous solution lithium ion secondary battery negative pole, electrolyte and battery, the active material of the cathode is one of crystallization hyrate of zinc tartrate and/or zinc tartrate or a variety of, and the electrolyte of the battery is the mixed aqueous solution of lithium tartrate aqueous solution or lithium tartrate and lithium hydroxide.It is high, environmentally friendly, inexpensive that the battery system is integrated with traditional zinc electrode specific energy, and the embedding lithium class material structure of lithium ion cell positive stablizes the advantages of good cycle, has avoided rocking chair type lithium ion secondary battery lithium intercalation compound negative electrode material the disadvantages of water system applied energy density is low, poor circulation and zinc electrode thermodynamic instability, readily soluble, dendrite in alkaline electrolyte cause service life short problem.The embedding dealkylation reaction mixing mechanism of precipitating-that double ion is cleverly utilized realizes the breakthrough of aquo-lithium ion battery application.
Description
Technical field
The invention belongs to field of chemical power source, and in particular to a kind of coordination polymer negative electrode material, electrolyte and comprising
The aqueous solution lithium ion secondary battery of the negative electrode material and electrolyte.
Background technique
Lithium ion non-aqueous secondary batteries are high with its specific energy, have extended cycle life, in mobile communication, digital camera, notebook
The fields such as computer have a wide range of applications.However the electrolyte that the lithium ion battery of business application uses is organic electrolyte,
Inflammable and explosive characteristic leads to have serious security risk in improper operation.In addition, the ionic conductivity ratio of nonaqueous electrolytic solution
Corresponding water system wants low 2 orders of magnitude, affects giving full play to for intercalation materials of li ions performance and battery performance；Organic electrolyte component
There is certain toxicity, and production cost is much higher accordingly, safety and cost problem limit the extensive of enlarged lithium ion
Using.
The Wu.Li of Jeff Dahn research group, Canada in 1994 delivers one on SCIENCE magazine with VO2It is negative
Pole, LiMn2O4For anode and with Li2SO4Or LiNO3Document of the aqueous solution as electrolyte, but its cycle performance is undesirable, energy
Metric density is also relatively low.Henceforth constantly there is researcher exploitation new material for aquo-lithium ion battery pilot study.
Negative electrode material is typically chosen intercalation potential in 2~3V (vs Li+/ Li) material.In this potential region have compared with
The intercalation materials of li ions of good chemical property is few, and relevant report is less, either reported barium oxide V2O3, vanadate
LiV3O8Or phosphoric acid titanium salt LiTi2(PO4) material etc. without exception show cyclicity difference and specific capacity common fault less than normal.
In terms of positive electrode, the Li with spinel structure1-xMnO4With the LiFePO of olivine structural4It will not be water-soluble
Send out insertion reaction protogenic in liquid, LiMnO4With the LiFePO of olivine structural4In Li2SO4Or LiNO3Aqueous solution is as electrolysis
Be in matter liquid it is stable, have good cyclical stability, LiCo1/3Ni1/3Mn1/3O2It is also shown in the lithium salts of pH=12
Preferable cyclical stability, it is clear that the key of Water-soluble lithium ion battery is the selection of negative electrode material.
In recent years more and more researchers begin trying metallic zinc be cathode, lithium salts (registered have lithium sulfate,
Lithium chloride, lithium nitrate, lithium acetate) and zinc salt (zinc sulfate, zinc chloride, zinc nitrate) mixed solution be electrolyte design water system
Lithium ion battery also shows high magnification and high circulation quality.
A kind of appearance of novel battery recently would be possible to change the pattern of energy-storage battery.Canadian University of Waterloo (CA) Waterloo, Ontario, N2L3GI Canada in
In June, 2012 discloses a kind of based on the exchange of electrolyte inner ion in battery periodical " Journal of Power Source "
The novel aqoue seconary battery " Rechargeable Hybrid Aqueous Batteries " of working principle, and provide
A kind of chargeable water system lithium zinc battery application example haveing excellent performance: using the spinelle manganic acid lithium material that is coated in graphite foil as
Anode, using stainless steel as inertia cathode, to be dissolved with the ZnCl of 4mol/l2Aqueous solution with the LiCl of 3mol/l is electrolyte,
For AGM cellular glass fibrous paper as diaphragm, obtaining a kind of average working voltage in 1.8V, service life cycle is more than 4000 times
Rechargeable battery, the theoretical energy density of the battery is 160Wh/kg, it is contemplated that actual energy density up to 50~80Wh/kg,
Its material cost is calculated also below lead-acid battery.However this electrochemical power source system substantially belongs to flow battery, 1. zinc
The electric discharge active material of electrode is dissolved in electrolyte, and such electrode process is controlled by liquid phase diffusing step, causes concentration polarization,
Inevitably cathode charge when generate dendroid dendrite, 2. use two or more electrolyte solutions, cause electrolyte it
Between the irreversible cross contamination diffuseed to form.Obvious this liquid stream type zinc load is difficult to be made into practical electrochemical cell.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of specific energy height, have extended cycle life, highly-safe, cheap polycomplexation
Close object negative electrode material, electrolyte, and the novel aqueous solution lithium ion battery comprising above-mentioned material combination.
The present invention proposes a kind of aquo-lithium ion secondary cell scheme of insoluble zinc, contains lithium in the electrolytic solution using a kind of
Ion and anion-tartrate anion of precipitating function are as novel electrolyte conductive agent.When electrode discharge, zinc be oxidized to sun from
Sub- Zn2+With the C in electrolyte4H4O6 2+Anion binding generate sediment insoluble in electrolyte and be attached to electrode surface (increasing
The strong invertibity of electrode reaction), the lithium ion in electrolyte, which is then embedded in the lattice of positive inlaid scheme, to be completed to discharge
Journey.When electrode charge, cathode zinc tartrate, which is reduced, resolves into zinc and tartrate ion, and zinc is deposited on electrode surface, winestone
Acid ion then meets with the lithium ion of deintercalation in positive electrode and is combined into electrolyte again, and composition of electrolyte does not become
Change, but concentration of electrolyte is varied.The Mechanism of electrochemical behaviors of anhydrous of the battery is unique, it can be understood as entire battery is by two and half electricity
Pond is constituted；Cathode half-cell realizes that electrochemical redox is anti-with traditional lead acid batteries, the dissolution precipitation mechanism of ickel-cadmium cell
It answers.Positive half-cell realizes electrochemical redox reaction by the embedding off line reason of lithium ion rocking chair.Battery of the invention belongs to molten
Solution precipitating-embedding de- mixing mechanism type aquo-lithium ion secondary cell.The battery uses single electrolyte aqueous, avoids electrolysis
The generation of cross contamination and side reaction between liquid polyion, effectively improves battery coulombic efficiency.Tartrate is usually used in plating
The addition composition of bright zinc, tartrate anion and Zn2+Coordination it is strong, the number that big cathodic polarization is conducive to nucleus increases, suppression
Nucleus persistently growing up in situ is made, the included tartrate group of this system is to have very much to the growth for preventing zinc dendrite
Benefit.
Coordination polymer is the complex without limit structure that metal ion and organic ligand are formed by self assembly,
It has tempting application prospect in light, electricity, magnetic, catalysis.
Jin Jing of Liaoning Normal University in 2007 et al. has synthesized a kind of Zn (II) coordination polymer using hydrothermal synthesis method
{[Zn(C4H4O6)(H2O)2]·2H2O}n, X-ray diffraction analysis has been carried out to the monocrystalline of the compound, it is determined that structure be by
Tartrate anion has coordination polymer of the 3D without limit structure as what sexadentate ligand and Zn (II) ion carried out coordination formation.2009
Macro gorgeous wait of the woods of Nian Bohai university chemistry university of chemical technology has synthesized a kind of new Zn based on tartaric acid at room temperature2+Coordination
Polymer, chemical molecular formula are as follows: { [Zn (C4H4O6)(H2O)]2·3H2O}n, pass through X-ray single crystal diffraction method, elemental analysis
And infrared spectroscopy characterizes its structure.The result shows that Zn in the polymer2+It is the distorted octahedra geometry of hexa-coordinate
Configuration, tartaric acid take two different coordination modes alternately connection Zn2+Ion forms two-dimensional layered structure.The polymer has
Photoluminescent property.Chinese patent Authorization Notice No. CN101550601B discloses zinc tartrate as ferroelectric function material and preparation side
Method, the molecular formula of the material of preparation are as follows: [Zn (H2O)(C4H4O6)2/2]·2H2O].Chinese patent Authorization Notice No.
CN101654408B discloses anhydrous zinc tartrate as ferroelectric function material and preparation method, the molecular formula of anhydrous zinc tartrate
Are as follows: [Zn (C4H4O6)].Jung Soo Seo etc. has good urge using the organic metal salt that D- tartaric acid and zinc ion are prepared
Change active (Jung Soo Seo et al.Nature 404 (2000) 982).Organic metal salt because light, electricity, magnetic, absorption and
The fields such as catalysis are with a wide range of applications and become research hotspot in recent years.But have no zinc tartrate as water system lithium from
Sub- cell negative electrode material and the document report of battery system application.
The present invention provides a kind of aqueous solution lithium ion secondary battery negative pole, which includes negative current collector and load
Negative electrode material on the negative current collector, wherein the negative electrode active material of the negative electrode material is zinc tartrate and/or winestone
One of crystallization hyrate of sour zinc is a variety of.
The aqueous solution lithium ion secondary battery negative pole provided according to the present invention, wherein the crystallization aquation of the zinc tartrate
Object may include substance represented by following molecular formula: [Zn (H2O)(C4H4O6)2/2]·2H2O]、[Zn(C4H4O6)(H2O)]2·
3H2O and [Zn (C4H4O6)(H2O)]2·2H2O.Wherein, [Zn (C4H4O6)(H2O)]2·3H2O and [Zn (C4H4O6)(H2O)]2·
2H2O is usually infinite multiple molecule aggregations and the form of polymer that is formed, is represented by { [Zn (C4H4O6)(H2O)]2·
3H2O}n{ [Zn (C4H4O6)(H2O)]2·2H2O}mWherein, the value of n and m is respectively depending on [Zn (C4H4O6)(H2O)]2·3H2O
Or [Zn (C4H4O6)(H2O)]2·2H2The amount of O.
The aqueous solution lithium ion secondary battery negative pole provided according to the present invention, wherein the negative electrode active material supports
Amount can be 2~20mg/cm2, preferably 5~15mg/cm2。
The aqueous solution lithium ion secondary battery negative pole provided according to the present invention, wherein the negative electrode active material, i.e. winestone
The crystallization hyrate of sour zinc and/or zinc tartrate can be monoclinic system, rhombic system or unformed.
On the other hand, the present invention also provides lithium tartrates to prepare answering in aqueous solution electrolyte of lithium-ion secondary battery
With.Wherein, the concentration of lithium tartrate can be 0.1~1.5mol/l, preferably 0.5~1.5mol/.Preferably, using winestone
The saturated aqueous solution of sour lithium is as electrolyte.It is further preferred that lithium hydroxide can also be contained in the electrolyte, the hydrogen
Lithia is used to the pH of electrolyte being adjusted to 7.6~13, preferably 7.6~9.
In another aspect, the battery includes battery case, electricity the present invention also provides a kind of aqueous solution lithium ion secondary battery
Pole group and electrolyte, electrode group and electrolyte are sealed in battery case, and the electrode group includes anode, diaphragm and cathode,
In, the cathode is cathode provided by the present invention.
The aqueous solution lithium ion secondary battery provided according to the present invention, wherein the electrolyte is lithium tartrate aqueous solution
Or the mixed aqueous solution of lithium tartrate and lithium hydroxide.Wherein, the concentration of lithium tartrate can be 0.1~1.5mol/l, excellent
It is selected as 0.5~1.5mol/l.When the electrolyte is the mixed aqueous solution of lithium tartrate and lithium hydroxide, the lithium hydroxide
For the pH of electrolyte to be adjusted to 7.6~13, preferably 7.6~9.That is, the main function of lithium hydroxide is to be used for
Adjust the pH value size of electrolyte.
The aqueous solution lithium ion secondary battery provided according to the present invention, wherein the anode may include plus plate current-collecting body
And it is supported on the positive electrode on the plus plate current-collecting body, the positive active material of the positive electrode can be LiMn2O4、
LiFePO4、LiCoPO4、LiCoO2、LiMnPO4、LiFeO2、LiMn0.2Fe0.8PO4、LiFe0.4Mn0.5Co0.1PO4、
LiCo0.19Ni0.81O2、LiNiO2、LiCo1/3Ni1/3Mn1/3O2、Li2FePO4F、LiMn1.5Ni0.5O4、Li1+x
(Fe0.2Ni0.2Mn0.6)1-xO2、Li1+x(Fe0.2Ni0.4Mn0.4)1-xO2And Li3V2(PO4)3One of or it is a variety of.Preferably, institute
Stating positive electrode can also include one or more doped chemicals selected from the following: Al, Zn, Nb, Zr, Co, Cr, Ni, Mn, Cu and
Mg。
The pole piece of the positive and negative electrode of aqueous solution lithium ion secondary battery provided by the invention can by by active material with lead
Electric agent (acetylene black, graphite, carbon nanotube, graphene, sub- titanium oxide etc.) bonding agent (Kynoar, LA132, polytetrafluoroethyl-ne
Alkene, CMC etc.) and dispersing agent (NMP, water etc.) mix in certain proportion after obtain phase in resulting slurry full-filling to collector
The pole piece answered.The collector for being used to prepare cathode of the present invention can be the common negative current collector material of zinc series alkaline cell, this
To this, there is no particular limitation for invention, for example, can be silver-colored net, brass screen, perforation plating indium copper strips, tin plating copper foil etc..Preferably,
Collector for cathode of the present invention is zinc foil.Plus plate current-collecting body can be traditional water system battery plus plate current-collecting body common used material,
Such as carbon paper, nickel screen, nickel foam, stainless steel foil etc..Being preferred for plus plate current-collecting body of the present invention is stainless steel foil.
The diaphragm of aqueous solution lithium ion secondary battery provided by the invention can be glass fibre, microporous polypropylene membrane, more
PP/PE plastics, polycthylene grafted film, the three acetic acid diaphragm of nylon fiber nonwoven, polyvinyl paper or porous polypropylene in hole.
The cathode of aqueous solution lithium ion secondary battery provided by the invention is by ZnC4H4O6/ Zn composition, anode is by LiMn2O4Or
LiFePO4Deng composition, electrochemistry expression formula is as follows:
(-)ZnC4H4O6∣Li2C4H4O6∣①LiMn2O4Or 2. LiFePO4Deng (+)
Electro-chemical reaction equations are as follows:
Negative reaction:
1. anode reaction:
Overall reaction:
2. anode hair is answered:
Overall reaction:
The basic principle of aqueous solution lithium ion secondary battery provided by the invention is as follows: with diaphragm by positive plate and negative electrode tab
It separates to dressing up battery, and injects electrolyte.Battery must charge first, and in charging, lithium ion is deviate from from solid phase anode,
Into electrolyte (liquid phase).Cathode zinc tartrate is reduced into zinc and is deposited on electrode surface, and tartrate anion takes off Zn2+To electrolyte
The transfer of (liquid phase) direction.It meets at this time with lithium ion and is combined into electrolyte.When electric discharge, cathodic reduction state zeroth order zinc is oxidized to
Zn2+Afterwards by the sexadentate ligand C as crab4H4O6 2-Occlusion generates insoluble precipitate and fixes at the electrode surface, electrolyte
In lithium ion be then embedded in positive inlaid scheme crystal.In entire charge and discharge process, lithium ion and tartaric acid are pertained only to
Root anion carries out liquid phase and solid phase transfer or embedding de- on corresponding pole piece.Therefore battery system of the invention is known as dissolving
Precipitating-embedding de- mixing mechanism type aqueous solution lithium ion secondary battery.In charge and discharge process, electrolyte composition does not change,
Only concentration changes, and is similar to lead-acid battery electrolyte sulfuric acid concentration and changes.
Aqueous solution battery system of the invention be secondary cell from traditional aqueous battery to nonaqueous lithium ion battery again to
Modern aqueous solution lithium is crossed over again from battery.The battery system is integrated with high traditional zinc electrode specific energy, environmental protection, inexpensive,
And the embedding lithium class material structure of lithium ion cell positive stablizes the advantages of good cycle, has avoided rocking chair type lithium ion secondary electricity
Pond lithium intercalation compound negative electrode material is the disadvantages of water system applied energy density is low, poor circulation and zinc electrode is in alkaline electrolysis
Thermodynamic instability, readily soluble, dendrite cause service life short problem in liquid.The embedding dealkylation reaction of precipitating-of double ion is cleverly utilized
Mixing mechanism realizes the breakthrough of aquo-lithium ion battery application.
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 is the charging and discharging curve figure of aqueous solution lithium ion secondary battery made from embodiment 1；
Fig. 2 is the charging and discharging curve figure of aqueous solution lithium ion secondary battery made from embodiment 2；
Fig. 3 is the charging and discharging curve figure of aqueous solution lithium ion secondary battery made from embodiment 3；
Fig. 4 is the charging and discharging curve figure of aqueous solution lithium ion secondary battery made from embodiment 4；
Fig. 5 is the charge and discharge cycles figure of aqueous solution lithium ion secondary battery made from embodiment 4.
Specific embodiment
The present invention is further described in detail With reference to embodiment, and the embodiment provided is only for explaining
The bright present invention, the range being not intended to be limiting of the invention.
(A) zinc tartrate negative electrode active material synthesis step used in following embodiment is as follows:
Weigh 0.6mol tartaric acid (C4H6O6) be dissolved in 1000ml deionized water, being configured to concentration is 0.6mol/l's
Solution for later use.Zinc nitrate (Zn (NO is weighed in the ratio of zinc ion and tartaric acid molar ratio 1: 33)2·6H2O), delay while stirring
Slowly zinc nitrate is added into preconfigured tartaric acid solution, stirs 40min, zinc nitrate, which is also added, to be finished and abundant molten
Solution, is filtered to remove insoluble matter, gained filtrate is zinc tartrate solution.Then the pH of filtrate is adjusted with the NaOH solution of 1mol/l
=6.0, filtrate stirs 1h under 50 DEG C of constant temperature, forms white turbid, after being cooled to room temperature and being aged 2h, filters, obtains
White powder crystal, is filtered to remove insoluble matter, and gained filtrate is zinc tartrate solution.It is small to place it in dehydration 6 in 150 DEG C of baking ovens
When, white powder is obtained, polished 300 mesh of mistake obtains the white anhydrous Zn (C that purity is not less than 99%4H4O6) powder,
Sealing storage, it is spare.
(B) zinc tartrate crystalline hydrate negative electrode active material synthesis step used in following embodiment is as follows:
Weigh 0.2mol L- (+)-tartaric acid (C4H6O6) be dissolved in 1000ml deionized water, being configured to concentration is
The solution for later use of 0.2mol/l；Zinc nitrate (Zn is weighed according to zinc ion and L- (+)-tartaric acid molar ratio 1: 2 ratio
(NO3)·6H2O), slowly zinc nitrate is added into prepared L- (+)-tartaric acid solution while stirring, stirs 30min
Afterwards, zinc nitrate is also added and finishes and sufficiently dissolve, and is filtered to remove insoluble matter, filtrate is placed in 40 DEG C of insulating box and stands 10 days
Colourless bulk crystals are obtained, molecular formula is [Zn (H2O)(C4H4O6)2/2]·2(H2O)].Crystal is placed in agate mortar and is ground
Mill, polished 300 mesh of mistake are spare.
Embodiment 1
It is positive active material that the present embodiment, which is described using zinc tartrate crystalline hydrate as negative electrode active material, LiMn2O4,
Lithium tartrate aqueous solution is the aqueous solution lithium ion secondary battery of electrolyte.
The preparation of cathode: weighing 2 grams of zinc tartrate crystalline hydrate, 0.15 gram of carbon nanotube, 0.1 gram of acetylene black respectively,
Be put into agate mortar mix it is finely ground.It weighs each 0.15 gram of bonding agent PVDF, LA132 and is successively dissolved in heating stirring in nmp solvent
Uniformly, it finely ground mixture will be mixed pours into above-mentioned solvent stirring and negative electrode slurry is made.Negative current collector selects 0.1 millimeter
Zinc foil, acetone and deionized water are alternately cleaned when use, and then negative electrode slurry is coated uniformly on zinc foil with glass bar, are passed through
Negative electrode tab, loading 9mg/cm is made in 80 DEG C of dryings, roll-in, 120 DEG C of dryings2。
The preparation of anode: 2 grams of commodity LiMn2O4,0.2 gram of carbon nanotube, 0.1 gram of acetylene black are weighed, is put into agate mortar
It mixes finely ground.It weighs 0.25 gram of bonding agent PVDF and is dissolved in that heating stirring in nmp solvent is uniform, then will mix finely ground mixing
Object pours into stirring in above-mentioned solvent and anode sizing agent is made.Plus plate current-collecting body selects 0.1 millimeter of graphite paper, stainless steel when use
Then anode sizing agent is coated uniformly on graphite paper, through 80 DEG C of dryings, roll-in, 120 DEG C of dryings by brush brush at hair side with glass bar
Positive plate, loading 21mg/cm is made2。
Diaphragm: AGM cellular glass fibrous paper is diaphragm.
Electrolyte: 1mol/l lithium tartrate aqueous solution adjusts pH=7.8 with lithium hydroxide.
Above-mentioned negative electrode tab, positive plate are separated with diaphragm and are assembled into rectangular cell, positive capacity is much larger than cathode, pours into
Stand 30 minutes after electrolyte, then carry out constant current charge-discharge performance test, by charging/discharging voltage be 1.3V~2.15V.
Fig. 1 is the charging and discharging curve figure of battery made from the present embodiment, open-circuit voltage 2.0V, and mean voltage is
1.732V.Zinc tartrate crystalline hydrate cathode charge specific capacity at 1C is 230mAh/g, specific discharge capacity 191.5mAh/
G, charge and discharge coulombic efficiency are 83.3%.
Embodiment 2
It is positive active material that the present embodiment, which is described using zinc tartrate as negative electrode active material, cobalt acid lithium, lithium tartrate water
Solution is the aqueous solution lithium ion secondary battery of electrolyte.
The preparation of cathode: 2 grams of zinc tartrate, 0.15 gram of activated carbon, 0.1 gram of acetylene black are weighed respectively, is put into agate mortar
Middle mixing is finely ground.Weighing each 0.15 gram of bonding agent PVDF, LA132, to be successively dissolved in heating stirring in nmp solvent uniform, and mixing is ground
Thin mixture pours into stirring in above-mentioned solvent and negative electrode slurry is made.Negative current collector selects the Foam silver of 0.2 millimeters thick, uses
When acetone and deionized water alternately clean, then negative electrode slurry is coated uniformly on Foam silver with glass bar, it is dry through 80 DEG C
Negative electrode tab, loading 12mg/cm is made in dry, roll-in, 120 DEG C of dryings2。
The preparation of anode: weighing 2 grams of cobalt acid lithium, 0.2 gram of graphite powder, 0.1 gram of acetylene black, is put into mix in agate mortar and grind
Carefully.It weighs 0.25 gram of bonding agent PVDF and is dissolved in that heating stirring in nmp solvent is uniform, then will mix finely ground mixture and pour into
Anode sizing agent is made in stirring in above-mentioned solvent.Plus plate current-collecting body selects the graphite paper of 0.1 millimeters thick, with stainless steel brush brush when use
At hair side, then anode sizing agent is coated uniformly on graphite paper with glass bar, is made through 80 DEG C of dryings, roll-in, 120 DEG C of dryings
Positive plate, loading 35mg/cm2。
Diaphragm: AGM cellular glass fibrous paper is diaphragm.
Electrolyte: 1mol/l lithium tartrate aqueous solution adjusts pH=11 with lithium hydroxide.
Above-mentioned negative electrode tab, positive plate are separated with diaphragm and are assembled into rectangular cell, positive capacity is much larger than cathode, pours into
Stand 30 minutes after electrolyte, then carry out constant current charge-discharge performance test, by charging/discharging voltage be 1.0V~2.22V.
Fig. 2 is the charging and discharging curve figure of battery made from the present embodiment, open-circuit voltage 2.05V, and mean voltage is
1.7709V.Cathode zinc tartrate specific discharge capacity at 1C is 233.7mAh/g, and charge and discharge coulombic efficiency is 67.13%.
Embodiment 3
It is positive active material that the present embodiment, which is described using zinc tartrate as negative electrode active material, LiFePO4, lithium tartrate
Aqueous solution is the aqueous solution lithium ion secondary battery of electrolyte.
The preparation of cathode: 2 grams of zinc tartrate, 0.15 gram of activated carbon, 0.1 gram of acetylene black are weighed respectively, is put into agate mortar
Middle mixing is finely ground.Weighing each 0.15 gram of bonding agent PVDF, LA132, to be successively dissolved in heating stirring in nmp solvent uniform, and mixing is ground
Thin mixture pours into stirring in above-mentioned solvent and negative electrode slurry is made.Negative current collector selects the zinc foil of 0.1 millimeters thick, when use
It is alternately cleaned, then negative electrode slurry is coated uniformly on zinc foil with glass bar, through 80 DEG C of dryings, rollers with acetone and deionized water
Pressure, 120 DEG C of dryings are cut into the negative electrode tab of 1cm × 2cm, loading 7mg/cm2。
The preparation of anode: 2 grams of commercial phosphoric acid iron lithium, 0.2 gram of carbon nanotube, 0.1 gram of acetylene black are weighed, agate mortar is put into
Middle mixing is finely ground.It weighs PVDF0.25 grams of bonding agent and is dissolved in that heating stirring in nmp solvent is uniform, then will mix finely ground mixing
Object pours into stirring in above-mentioned solvent and anode sizing agent is made.Plus plate current-collecting body selects the stainless steel foil of 0.05 millimeters thick, and when use is used
Stainless steel surface sanding is alternately cleaned with acetone and deionized water, is then uniformly applied anode sizing agent with glass bar by fine sandpaper
It overlays on stainless steel foil, is cut into 4cm × 5cm through 80 DEG C of dryings, roll-in, 120 DEG C of dryings and positive plate is made, loading is
19mg/cm2。
Diaphragm: the PP-PE composite porous film for taking 20 microns of thickness is diaphragm.
Electrolyte: 1mol/l lithium tartrate aqueous solution adjusts pH=8 with lithium hydroxide.
Above-mentioned negative electrode tab, positive plate are separated with diaphragm and are assembled into rectangular cell, stands 30 minutes after pouring into electrolyte, so
Afterwards carry out the test of constant current charge-discharge cycle performance, by charging/discharging voltage be 0.8V~1.6V.
Fig. 3 is that the open-circuit voltage of battery made from the present embodiment is 1.3V, mean voltage 1.16V.Cathode zinc tartrate
Charging capacity is 232.2mAh/g at 1C, and specific discharge capacity 225.5mAh/g, charge and discharge coulombic efficiency is 97.16%.
Embodiment 4
The present embodiment description is positive electrode active material by negative electrode active material, LiFePO4 of zinc tartrate crystalline hydrate
Matter, the aqueous solution lithium ion secondary battery that lithium tartrate aqueous solution is electrolyte.
The preparation of cathode: 2 grams of zinc tartrate crystalline hydrate, 0.15 gram of activated carbon, 0.1 gram of acetylene black are weighed respectively, is put
Enter mixed in agate mortar it is finely ground.Weighing each 0.15 gram of bonding agent PVDF, LA132, to be successively dissolved in heating stirring in nmp solvent equal
It is even, it finely ground mixture will be mixed pours into above-mentioned solvent stirring negative electrode slurry is made.Negative current collector selects 0.2 millimeters thick
Perforated zinc band, acetone and deionized water are alternately cleaned when use, and negative electrode slurry is then coated uniformly on perforation with glass bar
On zinc band, 1cm × 2cm negative electrode tab, loading 13mg/cm are cut into through 80 DEG C of dryings, roll-in, 120 DEG C of dryings2。
The preparation of anode: 2 grams of commercial phosphoric acid iron lithium, 0.2 gram of graphite powder, 0.1 gram of acetylene black are weighed, is put into agate mortar
It mixes finely ground.Weigh 0.25 gram of bonding agent CMC, 0.3 gram of PTFE (solid content 60%) is dissolved in deionized water solvent and stirring
It is even, it then will mix finely ground mixture and pour into above-mentioned solvent stirring anode sizing agent is made.Plus plate current-collecting body selects nickel foam,
Alternately cleaned with acetone and deionized water, then anode sizing agent be coated uniformly in nickel foam with glass bar, through 80 DEG C of dryings,
Roll-in, 120 DEG C of dryings are cut into 4cm × 5cm positive plate, loading 27mg/cm2。
Diaphragm: the PP-PE composite porous film for taking 20 microns of thickness is diaphragm.
Electrolyte: 1mol/l lithium tartrate aqueous solution adjusts pH=8.5 with lithium hydroxide.
Above-mentioned negative electrode tab, positive plate are separated with diaphragm and are assembled into rectangular cell, stands 30 minutes after pouring into electrolyte, so
Afterwards carry out the test of constant current charge-discharge cycle performance, by charging/discharging voltage be 0.8V~1.5V.
Fig. 4 is that the open-circuit voltage of battery made from the present embodiment is 1.2V, mean voltage 1.13V.Cathode zinc tartrate
Crystalline hydrate charging capacity at 1C is 200mAh/g, specific discharge capacity 195.1mAh/g, and charge and discharge coulombic efficiency is
97.5%.
Fig. 5 is battery charging and discharging cyclic curve figure made from the present embodiment 4, and discharge capacitance is after 44 circulations
93.48, charge and discharge coulombic efficiency is stablized 90% or more.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail.It should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (17)
1. the crystallization hyrate of zinc tartrate and/or zinc tartrate is preparing answering in aqueous solution lithium ion secondary battery negative pole
With the negative electrode material that, the cathode includes negative current collector and is supported on the negative current collector, wherein the negative electrode material
Negative electrode active material be one of crystallization hyrate of zinc tartrate and/or zinc tartrate or a variety of.
2. application according to claim 1, wherein the crystallization hyrate of the zinc tartrate includes following molecular formula institute table
The substance shown: [Zn (H2O)(C4H4O6)2/2]·2H2O]、[Zn(C4H4O6)(H2O)]2·3H2O and [Zn (C4H4O6)(H2O)]2·
2H2O。
3. application according to claim 1, wherein the loading of the negative electrode active material is 2~20mg/cm2。
4. application according to claim 3, wherein the loading of the negative electrode active material is 5~14mg/cm2。
5. application of the lithium tartrate in the electrolyte for preparing aqueous solution lithium ion secondary battery, wherein the aqueous solution lithium ion
The negative electrode active material of the cathode of secondary cell is one of crystallization hyrate of zinc tartrate and/or zinc tartrate or more
Kind.
6. application according to claim 5, wherein the concentration of lithium tartrate is 0.1~1.5mol/l.
7. application according to claim 6, wherein the concentration of lithium tartrate is 0.5~1.5mol/l.
8. application according to claim 5, wherein also contain lithium hydroxide in the electrolyte, the lithium hydroxide is used
In the pH of electrolyte is adjusted to 7.6~13.
9. application according to claim 8, wherein the lithium hydroxide is used to the pH of electrolyte being adjusted to 7.6~9.
10. a kind of aqueous solution lithium ion secondary battery, which includes battery case, electrode group and electrolyte, electrode group and electricity
Solution liquid is sealed in battery case, and the electrode group includes anode, diaphragm and cathode, wherein the cathode includes negative pole currect collecting
Body and the negative electrode material being supported on the negative current collector, which is characterized in that the negative electrode active material of the negative electrode material is
One of crystallization hyrate of zinc tartrate and/or zinc tartrate is a variety of.
11. aqueous solution lithium ion secondary battery according to claim 10, wherein the electrolyte is that lithium tartrate is water-soluble
The mixed aqueous solution of liquid or lithium tartrate and lithium hydroxide.
12. aqueous solution lithium ion secondary battery according to claim 11, wherein the concentration of lithium tartrate be 0.1~
1.5mol/l。
13. aqueous solution lithium ion secondary battery according to claim 12, wherein the concentration of lithium tartrate be 1~
1.5mol/l。
14. aqueous solution lithium ion secondary battery according to claim 11, wherein when the electrolyte be lithium tartrate with
When the mixed aqueous solution of lithium hydroxide, the lithium hydroxide is used to the pH of electrolyte being adjusted to 7.6~13.
15. aqueous solution lithium ion secondary battery according to claim 14, wherein the lithium hydroxide is used for electrolyte
PH be adjusted to 7.6~9.
16. aqueous solution lithium ion secondary battery described in any one of 0 to 15 according to claim 1, wherein the anode includes
Plus plate current-collecting body and the positive electrode being supported on the plus plate current-collecting body, the positive active material of the positive electrode are
LiMn2O4、LiFePO4、LiCoPO4、LiCoO2、LiMnPO4、LiFeO2、LiMn0.2Fe0.8PO4、LiFe0.4Mn0.5Co0.1PO4、
LiCo0.19Ni0.81O2、LiNiO2、LiCo1/3Ni1/3Mn1/3O2、Li2FePO4F、LiMn1.5Ni0.5O4And Li3V2(PO4)3In one
Kind is a variety of.
17. aqueous solution lithium ion secondary battery according to claim 16, wherein the positive electrode further include selected from
Under one or more doped chemicals: Al, Zn, Nb, Zr, Co, Cr, Ni, Mn, Cu and Mg.
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| CN109980231B (en) * | 2017-12-28 | 2022-05-06 | 银隆新能源股份有限公司 | Slurry coated on current collector of lithium ion battery and application of slurry |
| CN108172911A (en) * | 2018-01-11 | 2018-06-15 | 武汉大学 | A kind of full vanadium Water-soluble lithium ion battery |
| CN111653834B (en) * | 2020-06-05 | 2021-10-08 | 恩力能源科技(安徽)有限公司 | Aqueous electrolyte, aqueous metal ion battery, and method for producing same |
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| JPH06223830A (en) * | 1993-01-21 | 1994-08-12 | Fuji Photo Film Co Ltd | Lithium secondary battery |
| CN102709553A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Positive electrode material and synthetic method thereof |
| CN103748710A (en) * | 2011-08-23 | 2014-04-23 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| CN105206832A (en) * | 2015-08-27 | 2015-12-30 | 张家港智电芳华蓄电研究所有限公司 | Sintering preparation method for zinc anode material |
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|---|---|---|---|---|
| JPH06223830A (en) * | 1993-01-21 | 1994-08-12 | Fuji Photo Film Co Ltd | Lithium secondary battery |
| CN103748710A (en) * | 2011-08-23 | 2014-04-23 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| CN102709553A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Positive electrode material and synthetic method thereof |
| CN105206832A (en) * | 2015-08-27 | 2015-12-30 | 张家港智电芳华蓄电研究所有限公司 | Sintering preparation method for zinc anode material |
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