CN107732236B - Utilize the method for siderite hydrothermal synthesis anode material for lithium-ion batteries - Google Patents
Utilize the method for siderite hydrothermal synthesis anode material for lithium-ion batteries Download PDFInfo
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- CN107732236B CN107732236B CN201711070931.9A CN201711070931A CN107732236B CN 107732236 B CN107732236 B CN 107732236B CN 201711070931 A CN201711070931 A CN 201711070931A CN 107732236 B CN107732236 B CN 107732236B
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- siderite
- phosphoric acid
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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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- 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 invention discloses a kind of methods using siderite hydrothermal synthesis anode material for lithium-ion batteries, siderite is dissolved in phosphoric acid,diluted first and obtains the solution of iron by it, and then lithium ion battery anode material lithium iron phosphate can be obtained in the solution of iron and lithium hydroxide hydro-thermal reaction.Phosphoric acid is directly added in the present invention in siderite, the iron of siderite is directly dissolved in phosphoric acid by the concentration and reaction temperature of control phosphoric acid and time, then hydrogen peroxide is added, LiFePO4 is obtained by hydro-thermal reaction, LiFePO4 after reaction exists in the form of precipitating in phosphoric acid, directly lithium ion battery anode material lithium iron phosphate just can be obtained in filtering, it is not only omitted so in advance with the process of iron in hydrochloric acid or sulfuric acid leaching siderite, it reduces costs, other impurity for being unfavorable for battery performance are not introduced, the electric conductivity of battery is improved.
Description
Technical field
The invention belongs to electrochemical field, the method for preparing the sub- cell positive material of lithium ion especially with siderite.
Background technique
Lithium ion battery is the new generation of green high-energy battery of performance brilliance, it has also become the emphasis of hi-tech development it
One, and the LiFePO4 synthetic method as anode material for lithium-ion batteries is the developing most important thing.Currently with sparring
The method of mine synthesizing iron lithium phosphate battery is, first by siderite using addition oxidant and phosphorus after sulfuric acid, hydrochloric acid or nitric acid dissolution
Acid or phosphate reaction generate precursor of lithium ionic cell positive material ferric phosphate, and ferric phosphate is synthesized with lithium carbonate and C sintering again
LiFePO4.Such as:
Chinese Patent Application No. 201210591476.8 discloses a kind of lithium ion battery anode material lithium iron phosphate forerunner
Siderite first using sulfuric acid or salt Ore Leaching and is adjusted solution concentration by the preparation method of body, and hydrogen peroxide or ozone is then added
Oxidant and precipitating reagent make magnesium and manganese member beneficial to electrochemical performances of lithium iron phosphate in siderite by controlling synthesis condition
Element is selectively entered precipitating, up to ferric lithium phosphate precursor after drying.
Chinese Patent Application No. 200810031119.3 discloses a kind of comprehensive utilization ilmenite and prepares LiFePO4 forerunner
The method of body: the mining Ore Leaching of ferrotianium filters to get filtrate, in a certain amount of other sources of iron of dissolved in filtrate, so that mixing is molten
It is 0.0005-0.5 that the concentration of Fe, which is the molar ratio of 0.01-3mol/L, Ti and Fe, in liquid；Suitable oxygen is added into mixed solution
Agent, with the pH=1.5-6.0 of the aqueous solution regulation system of alkali, so that part iron and certain foreign ions are co-precipitated, filtering is obtained
To filtrate；Precipitating reagent (0.01-6mol/L) is added into filtrate, and the pH=4.0-14.0 of the aqueous solution regulation system with alkali,
10min-24h is reacted in 10-90 DEG C of stirred reactor, is filtered, washed, will be deposited in after being dried at 50-150 DEG C in air
1-24h is calcined at middle 300-800 DEG C up to presoma-doping type metallic element of lithium ion battery anode material lithium iron phosphate
Di-iron trioxide.
Although the LiFePO4 chemical property for the method preparation that above-mentioned two document is recorded is good, lacked there is also following
It falls into, first is that leaching the iron in siderite due to needing to be added acid, so long technical process, combined coefficient is low；Second is that due to adding
Enter sulfuric acid, hydrochloric acid or nitric acid, introduces the impurity element S O for influencing battery performance4 2-、CL-And NO3 -Deng.
It is added without sulfuric acid, hydrochloric acid or nitric acid at present, molysite, lithium salts and phosphoric acid is directly used, synthesizes phosphorus under hydrothermal conditions
Sour iron lithium, for example, Chinese Patent Application No. 201110045252.2 disclose one kind increase substantially low-temperature hydrothermal synthesis lithium from
Sub- cell positive material LiFePO4Has the method for excellent electrochemical performance, it is by lithium salts, molysite and phosphoric acid according to certain
Order of addition and proportion, prepare pulpous state precursor in water, a certain amount of organic solvent be then added, then in hydro-thermal item
The nanometer LiFePO with excellent chemical property is prepared under part4Positive electrode.The patent raw material uses soluble ferric iron salt, can
Producing for dissolubility molysite consumes a large amount of energy, increases reaction step.
China Patent Publication No. CN104817059A discloses one kind and prepares battery-grade iron phosphate by iron powder and phosphatase reaction
Method, it is to mix iron powder with phosphoric acid,diluted, reaction generate Fe (H2PO4)2, oxidizing generation ferric phosphate is then added
Precipitating, is filtered, is dried to obtain high-purity battery-grade iron phosphate i.e. Iron phosphate (FePO4) dihydrate；Iron phosphate (FePO4) dihydrate is metastrengite
The nano-sheet crystal of (fosfosiderite) crystal form.The technology of the disclosure has the disadvantage that first is that since main raw material is iron powder,
Common knowledge, iron powder are not nature naturally occurrings, are a kind of regrowths, need to make steel, and steel-making is that a comparison is multiple
Miscellaneous process will expend a large amount of electric energy and generate a large amount of pollution, if removing synthesizing lithium ion battery just with a kind of regrowth
This kind of certainly not recommendable good method of pole material；Second is that generating hydrogen during the reaction, hydrogen is a kind of easy
Explosive gas is fired, when reaching certain proportion in air, encountering open fire can explode, this not only gives entire process to bring
Harmfulness also requires operative employee to have very high operative skill.Thus, technology disclosed in the document can not be widely applied and
Industrialization does not meet current energy-saving and environment-friendly policy yet.
Summary of the invention
In order to overcome it is existing prepare long technical process existing for LiFePO4 technology, combined coefficient is low, and danger coefficient height is not
Technological deficiency easy to operate and containing impurity element, the present invention provide it is a kind of using siderite hydrothermal synthesis lithium ion battery just
The method of pole material.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A method of utilizing siderite hydrothermal synthesis anode material for lithium-ion batteries, which is characterized in that
Step 1: dissolution siderite
Phosphoric acid is directly added into siderite, it is desirable that the concentration of phosphoric acid is 0.2-3mol/L, it is desirable that iron and pure phosphoric acid rub
You are than being 2:(4-8), reaction temperature is 0-100 DEG C, reaction time 1-10h, and after sufficiently reacting, the molten of iron is obtained by filtration
Liquid, chemical equation are as follows:
FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
Step 2: the solution of iron and lithium hydroxide hydro-thermal reaction
It is directly added into lithium hydroxide in the solution of iron, sufficiently obtains LiFePO4 precipitating after reaction under hydrothermal conditions,
Lithium ion battery anode material lithium iron phosphate can be obtained in filtering, and LiFePO4 is washed with deionized, dries；It is required that iron and hydrogen
Lithia molar ratio is 1:(1-4), hydrothermal temperature is 100-300 DEG C, reaction time 5-15h, chemical equation are as follows:
Fe2++2(H2PO4)-+ LiOH=LiFePO4↓+H2O+H3PO4。
The material ferric lithium phosphate of technique preparation is as anode through the invention, using graphite as cathode, makes lithium-ion electric
Pond.
Illustrate advantages of the present invention below according to reaction mechanism:
Phosphoric acid is directly added in the present invention in siderite, makes sparring by the concentration and reaction temperature of control phosphoric acid and time
The iron of mine is directly dissolved in phosphoric acid, and hydrogen peroxide is then added by hydro-thermal reaction and obtains LiFePO4, the LiFePO4 after reaction
Exist in the form of precipitating in phosphoric acid, lithium ion battery anode material lithium iron phosphate just can be obtained in directly filtering, so not only
It is omitted in advance with the process of iron in hydrochloric acid or sulfuric acid leaching siderite, reduces costs, do not introduce other and be unfavorable for battery
The impurity of performance improves the electric conductivity of battery.
The raw material that the present invention utilizes is siderite, and siderite is a kind of more extensive mineral of distribution, can be used as iron ore
Stone refines iron, with siderite is directly dissolved in phosphoric acid, not only eliminates the energy consumption step that iron ore refines iron, realizes lithium ion
The purpose that cell positive material is directly obtained from nature, and siderite is easier for iron powder and phosphatase reaction,
Improve the feasibility of reaction.
It is the CO that colorless and odorless is odorless at normal temperature that the present invention, which adopts the gas generated during the reaction,2Gas, CO2Gas
Human body is not injured, CO that is easily operated without combustibility, and generating2Play the role of agitating solution, increases sparring
The activity of mine further improves the feasibility of reaction
In short, the present invention be it is a kind of low energy consumption, safety coefficient is high, convenient for the anode material for lithium-ion batteries for preparing of popularization
Method.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of one LiFePO4 of the embodiment of the present invention.
Fig. 2 is X-ray powder diffraction (XRD) figure of one LiFePO4 of the embodiment of the present invention.
Fig. 3 is scanning electron microscope (SEM) figure of the embodiment of the present invention diphosphonic acid iron lithium.
Fig. 4 is X-ray powder diffraction (XRD) figure of the embodiment of the present invention diphosphonic acid iron lithium.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.
Embodiment one
Embodiment one is by taking the siderite of the ferric carbonate containing 1mol as an example, and the concentration of phosphoric acid is 3mol/L, and specific preparation method is:
Step 1: dissolution siderite
It is 2:4 according to the molar ratio of iron and pure phosphoric acid, is directly added into siderite with H3PO is calculated as the phosphoric acid of 2mol, instead
Answering temperature is 70 DEG C, reaction time 2h, and after sufficiently reacting, the solution of iron, chemical equation is obtained by filtration are as follows:
FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
Step 2: the solution of iron and lithium hydroxide hydro-thermal reaction
It is 1:4 according to iron and lithium hydroxide molar ratio, 4moL lithium hydroxide is directly added into the solution of iron, in hydro-thermal item
LiFePO4 precipitating is obtained after sufficiently reacting under part, lithium ion battery anode material lithium iron phosphate, ferric phosphate can be obtained in filtering
Lithium washs through deionized water, is dry, and above-mentioned hydrothermal temperature is 200 DEG C, reaction time 8h.Reaction equation are as follows:
Fe2++2(H2PO4)-+ LiOH=LiFePO4↓+H2O+H3PO4
The scanning electron microscope and X-ray powder diffraction figure of LiFePO4 prepared by embodiment two are shown in Fig. 1-2 respectively.
Using LiFePO4 prepared by embodiment two as anode, graphite is cathode, and can be fabricated to cell voltage is 3V,
18650 battery capacities are1300mAThe lithium ion battery of h.
Embodiment two
For embodiment two by taking the siderite of the ferric carbonate containing 1mol as an example, the concentration of phosphoric acid is 0.2mol/L, specific preparation method
It is:
Step 1: dissolution siderite
It is 2:8 according to the molar ratio of iron and phosphorus, is directly added into siderite with H3The phosphoric acid that PO4 is calculated as 4mol, instead
Answering temperature is 50 DEG C, reaction time 5h, and after sufficiently reacting, the solution of iron, chemical equation is obtained by filtration are as follows:
FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
Step 2: the solution of iron and lithium hydroxide hydro-thermal reaction
It is 1:1 according to iron and lithium hydroxide molar ratio, 1moL lithium hydroxide is directly added into the solution of iron, in hydro-thermal item
LiFePO4 precipitating is obtained after sufficiently reacting under part, lithium ion battery anode material lithium iron phosphate, ferric phosphate can be obtained in filtering
Lithium washs through deionized water, is dry.Wherein hydrothermal temperature is 150 DEG C, reaction time 10h.Reaction equation are as follows:
Fe2++2(H2PO4)-+ LiOH=LiFePO4↓+H2O+H3PO4
The scanning electron microscope and X-ray powder diffraction figure of LiFePO4 prepared by embodiment two are shown in Fig. 3-4 respectively.
LiFePO4 is prepared as anode using embodiment two, graphite is cathode, and can be fabricated to cell voltage is 3V,
18650 battery capacities are the lithium ion battery of 1300mAh.
Claims (1)
1. a kind of method using siderite hydrothermal synthesis anode material for lithium-ion batteries, which is characterized in that
Step 1: dissolution siderite
Phosphoric acid is directly added into siderite, it is desirable that the concentration of phosphoric acid is 0.2-3mol/L, it is desirable that the molar ratio of iron and pure phosphoric acid
For 2:(4-8), reaction temperature is 0-100 DEG C, reaction time 1-10h, and after sufficiently reacting, the solution of iron is obtained by filtration, changes
Learn reaction equation are as follows:
FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
Step 2: the solution of iron and lithium hydroxide hydro-thermal reaction
It is directly added into lithium hydroxide in the solution of iron, sufficiently obtains LiFePO4 precipitating, filtering after reaction under hydrothermal conditions
Lithium ion battery anode material lithium iron phosphate can be obtained, LiFePO4 is washed with deionized, dries；It is required that iron and hydroxide
Lithium molar ratio is 1:(1-4), hydrothermal temperature is 100-300 DEG C, reaction time 5-15h, chemical equation are as follows:
Fe2++2(H2PO4)-+ LiOH=LiFePO4↓+H2O+H3PO4。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101047242A (en) * | 2007-03-12 | 2007-10-03 | 胜利油田华鑫石油材料有限公司 | Method for preparing equal dispersion ferric phosphate lithium nano crystal by hydrothermal synthetis method |
| CN101279727A (en) * | 2008-05-20 | 2008-10-08 | 上海大学 | Low-temperature hydro-thermal synthesis for nano-lithium iron phosphate |
| CN103022491A (en) * | 2012-12-31 | 2013-04-03 | 广西地博矿业集团股份有限公司 | Method for preparing lithium iron phosphate precursor for positive pole material of lithium-ion battery |
| CN103956485A (en) * | 2014-01-21 | 2014-07-30 | 武汉理工大学 | Lithium iron phosphate electrode material having three-dimensional hierarchical structure, and preparation method thereof |
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2017
- 2017-11-03 CN CN201711070931.9A patent/CN107732236B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101047242A (en) * | 2007-03-12 | 2007-10-03 | 胜利油田华鑫石油材料有限公司 | Method for preparing equal dispersion ferric phosphate lithium nano crystal by hydrothermal synthetis method |
| CN101279727A (en) * | 2008-05-20 | 2008-10-08 | 上海大学 | Low-temperature hydro-thermal synthesis for nano-lithium iron phosphate |
| CN103022491A (en) * | 2012-12-31 | 2013-04-03 | 广西地博矿业集团股份有限公司 | Method for preparing lithium iron phosphate precursor for positive pole material of lithium-ion battery |
| CN103956485A (en) * | 2014-01-21 | 2014-07-30 | 武汉理工大学 | Lithium iron phosphate electrode material having three-dimensional hierarchical structure, and preparation method thereof |
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