CN100405638C - Anode material of lithium ion battery in use for safety type miner's lamp, and preparation method - Google Patents

Anode material of lithium ion battery in use for safety type miner's lamp, and preparation method Download PDF

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Publication number
CN100405638C
CN100405638C CNB200510110085XA CN200510110085A CN100405638C CN 100405638 C CN100405638 C CN 100405638C CN B200510110085X A CNB200510110085X A CN B200510110085XA CN 200510110085 A CN200510110085 A CN 200510110085A CN 100405638 C CN100405638 C CN 100405638C
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preparation
anode material
lithium
safety type
lamp
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CN1761090A (en
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赖春艳
解晶莹
刘辉
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The present invention relates to an anode material of a lithium ion battery for a safety mineral lamp, which is characterized in that LiFePO4 prepared by adopting a high-temperature solid phase method is an active material of a battery with an olivine-shaped structure. When the LiFePO4 is used as the anode of the lithium ion battery for the mineral lamp, the characteristics of simple preparation technology, low price, high safety performance and good environmental protection can be fully performed. The lithium ion battery for the mineral lamp (showed in a drawing 5) using the LiFePO 4 as the anode material is packed and manufactured by aluminum plastic and can pass various security tests, and the LiFePO4 is the anode material of the lithium ion battery for the mineral lamp with an application prospect.

Description

Anode material for lithium-ion batteries of a kind of use for safety type miner's lamp and preparation method thereof
Technical field
The present invention relates to anode material for lithium-ion batteries of a kind of use for safety type miner's lamp and preparation method thereof, belong to mine lamp and use the lithium ion battery field.
Background technology
Mine lamp is the mine lighting instrument of coal miner indispensability, and its fail safe and quality and Safety of Coal Mine Production are closely related.At present, mine lamp mainly adopts lead-acid battery as power supply, lead-acid battery is short except having production cost height, average life span---400 circulations of less than, difficultly safeguard, quality heavy---2kg, volume big---12.5cm * 3.4cm * 19.5cm, carry outside the shortcomings such as inconvenience, also leakage causes acid corrosion easily, environmental pollution is serious, adds many difficulties for miner's operate as normal and life.In order to solve lead-acid battery as the problem that exists in the mine lamp power use, the someone proposes to use lithium ion battery to replace lead-acid battery as mine lamp power (patent 03119650.0).Compare with lead-acid battery, it is big that lithium ion battery has energy density, and volume is little, in light weight, long service life, and self-discharge rate is low, and can adapt to high humility and the intensive advantages such as mal-condition of dust in the mine.But present commercial anode material for lithium-ion batteries mainly adopts lithium and cobalt oxides and lithium nickel oxide, these material cost height, and in long-term cyclic process, the oxygen that electrode reaction discharges may cause safety problem with the electrolyte effect.Because mineral light requires highly to the fail safe aspect, thereby needs a kind of cost low, the anode material for lithium-ion batteries that security performance is good is guaranteed the safe handling of mine lamp.Simultaneously, the forward voltage drop 3.0～4.0V of the voltage platform of this positive electrode LED (the light emitting diode light-emitting diode) cold light source that also will use with safety miner's lamp is complementary.
Summary of the invention
At above problem, the object of the invention is to provide a kind of security performance good, with low cost mine lamp anode material for lithium-ion batteries LiFePO 4And preparation method thereof.
Mine lamp of the present invention anode material for lithium-ion batteries LiFePO 4The technology path that adopts is: high temperature solid-state method, and concrete technology path is as follows:
1, raw material is that 1: 1: 1 ratio is prepared burden in atomic ratio Li: Fe: P, is that ball-milling medium mixes in ball grinder with ethanol, utilizes ultrasonic wave to disperse then several minutes, is beneficial to the synthetic thinner and uniform powder product for preparing;
2, move in the horizontal chamber furnace (oven) behind the raw material drying that mixes, adopt two sections high temperature solid state reactions, heat a few hours down at 300～400 ℃ earlier, form the presoma of product;
3, the product presoma taking-up ball milling a few hours that generate;
4, will grind good material once more and put into horizontal chamber furnace (oven),, can obtain LiFePO 600～800 ℃ of following roasting a few hours 4Material.
Described raw material comprises the lithium source, source of iron and phosphorus source.LiOHH can be selected in the lithium source 2O or Li 2CO 3, the optional FeC of source of iron 2O 4H 2O or ferrous acetate, the optional NH in phosphorus source 4H 2PO 4Or (NH 4) 2HPO 4
Described ball milling environment is an air atmosphere, and the ball milling time was generally 5～10 hours; Solvent used during ball milling is volatile, inexpensive, nontoxic organic solvent, as ethanol;
Described ultrasonic wave disperses to be meant the dispersion in Ultrasound Instrument, and frequency is 50KHz, and jitter time was generally 20-60 minute;
The synthetic processing of described lower temperature is meant that under protective atmosphere temperature is to heat-treat between 300～400 ℃ (recommended temperature is 320～360 ℃), and purpose is that the organic salt of use decomposes or the aquo-compound dehydration, and the reaction time was at 5～8 hours;
Described high-temperature process is meant the high temperature sintering reaction of carrying out under protective atmosphere, the reaction time, reaction temperature was between 600～800 ℃ between 20～30 hours, and recommending sintering temperature is 700～780 ℃;
Described protective atmosphere can be N 2, Ar or Ar inert gas and H 2The mist of reducing gas, H 2Ratio be 5～10Vol%;
Described heating rate can be 5～30 ℃/min;
The present invention adopts the mine lamp anode material for lithium-ion batteries LiFePO of high temperature solid-state method preparation 4, compare with current material, have following beneficial effect:
1, positive electrode LiFePO 4The charging/discharging voltage window be 3.3～3.6V, this interval coincide with the present mine lamp forward voltage drop 3.0～4.0V with LED (light emitting diode light-emitting diode) cold light source in ten minutes, and discharge voltage is very steady, and stable operating voltage can be provided;
2, the LiFePO of olivine structural 4Have good structural stability, change in volume only is 6.8% in charge and discharge process, and the stable circulation performance is good, and no oxygen produces in the discharge process, makes it to have the characteristics of high security;
3, LiFePO 4Cationic dissolving does not take place during high temperature, but 60 ℃-80 ℃ down equal operate as normal, has good high temperature stability performance;
4, LiFePO 4Be environment-friendly material, aboundresources and low price.Prepared LiFePO 4The particle diameter of powder is 1-2 μ m.
Description of drawings
Fig. 1 is anode material for lithium-ion batteries LiFePO among the embodiment 1 4X-ray diffractogram.
Fig. 2 is LiFePO among the embodiment 1 4Electron scanning micrograph.
Fig. 3 is the LiFePO among the embodiment 1 4Cyclic voltammetry curve figure.
Fig. 4 is LiFePO among the embodiment 1 4Charging and discharging curve figure.
Fig. 5 contains LiFePO among the embodiment 4 4The mine lamp lithium ion battery schematic appearance of positive electrode.
Fig. 6 is the A-A cross-sectional view of Fig. 5.
Embodiment
Below in conjunction with accompanying drawing, invention is further described by embodiment.
Embodiment 1:
With chemical pure FeC 2O 4H 2O, NH 4H 2PO 4, LiOHH 2O is a raw material, is that 1: 1: 1 ratio is prepared burden in atomic ratio Li: Fe: P, is that solvent mixes in ball grinder with ethanol, ball milling incorporation time 5 hours, and ultrasonic wave disperseed 30 minutes then.Slurry after mixing is air drying 3 hours, finishes to the ethanol volatilization.Dried material is put into program control horizontal chamber furnace (oven) and is handled with two sections high temperature solid-state methods, and processing procedure feeds inert gas shielding all the time.Adopt temperature programming, at first at the uniform velocity be warming up to 300 ℃, heating rate is 5 ℃/min, isothermal reaction is 6 hours then, takes out sample and grinds 2h, places horizontal chamber furnace (oven) to be warming up to 750 ℃ again, roasting 24 hours, after question response finished, sample naturally cooled to room temperature, can make anode active material of lithium ion battery LiFePO 4Fig. 1 is the X-ray diffractogram of this material, and (numbering: 83-2092) card is corresponding fully, there is no other impurity peaks and occurs, and characterizing prepared material thing phase composition is olivine-type LiFePO with PDF in the diffraction maximum position 4Fig. 2 is the scanning electron micrograph of this material, and surface topography is analyzed the display material particle diameter and is about 1～2 μ m.LiFePO 4: acetylene black: PVDF (polyvinylidene fluoride) is 85%: 8%: 7%, is solvent with NMP (N-methyl pyrrolidone), makes uniform sizing material by magnetic agitation, is coated on the aluminium foil, prepares positive plate.In being full of the glove box of argon gas, be negative pole with the metal lithium sheet, adopt to contain 1M LiPF 6/ EC (cyclic carbonate)+DMC (dimethyl carbonate) (1: 1) organic solution is assembled into CR2025 type button cell and tests its performance as electrolyte; Cyclic voltammetric carries out on the CHI660B electrochemical workstation, and as shown in Figure 3, this material has a reduction peak about 3.3V, oxidation peak is arranged near 3.55V, and first circulation and second circulation have good repeatability.The constant current charge-discharge test of battery is carried out on Shenzhen road China's battery test system (range 5V/5mA), and as shown in Figure 4, material has charge and discharge platform very stably.
Embodiment 2:
With chemical pure FeC 2O 4H 2O, (NH 4) 2HPO 4, Li 2CO 3Being raw material, is that 1: 1: 1 ratio is prepared burden in atomic ratio Li: Fe: P, and all the other steps are with embodiment 1.The LiFePO for preparing 4Material property is suitable with embodiment 1.
Embodiment 3:
With chemical pure ferrous acetate, NH 4H 2PO 4, LiOHH 2O is a raw material, is that 1: 1: 1 ratio is prepared burden in atomic ratio Li: Fe: P.Two sections heating-up temperatures are respectively 380 ℃ and 780 ℃, and all the other steps are with embodiment 1.Prepare LiFePO 4The powder body material performance is close with embodiment 1.
Embodiment 4:
With gained positive electrode LiFePO 4Be used for the mine lamp lithium ion battery, make the polymer Li-ion battery of plastic-aluminum flexible packing, have very good performance.The prepared cell schematic diagram as shown in Figure 5.Mine lamp polymer Li-ion battery positive pole 6, barrier film 3, negative pole 7 and aluminium plastic composite packaging film 10, anodal 6 and negative pole 7 separate by barrier film, end at positive pole 6 and negative pole 7 is provided with both positive and negative polarity lug 8,9, is provided with aluminium collector 1 near anodal 6, be provided with copper collector 5 near negative pole 7, the outside adopts aluminum-plastic composite membrane 10 packings to form.
Above-mentioned positive active material 2 and negative electrode active material 4 directly are coated on aluminium collector 1, copper collector 5 grids, and positive plate 6, negative plate 7 and membrane layer 3 are wound on together, and controllable thickness is in 0.38mm.Positive active material wherein is LiFePO 4
With LiFePO 4For the mine lamp of positive active material assembling can be by various security tests with aluminum-plastic packaged lithium ion battery.

Claims (7)

1. the preparation method of a use for safety type miner's lamp anode material for lithium-ion batteries is characterized in that adopting two sections high temperature solid-state to handle, and processing step is:
(1) presses LiFeP 4Atomic ratio Li: Fe: P is that 1: 1: 1 ratio is prepared burden, and is medium with the alcohol solvent, carries out ultrasonic wave after ball milling mixes again and disperses;
(2) carry out two sections high temperature solid-state methods processing with moving into heating furnace behind the even scattered raw material drying of step (1), detailed process is:
(a) heating generates the product presoma under 300～400 ℃ of high temperature and protective atmosphere;
(b) from heating furnace, take out presoma, ball milling 2～5 hours;
(c) presoma behind the ball milling is put into once more heating furnace and under 600～800 ℃ and protective atmosphere, carried out roasting.
2. by the preparation method of the described use for safety type miner's lamp anode material for lithium-ion batteries of claim 1, it is characterized in that ultrasonic jitter time is 20-60 minute, used supersonic frequency is 50KHz.
3. by the preparation method of the described use for safety type miner's lamp anode material for lithium-ion batteries of claim 1, the temperature that it is characterized in that generating the product presoma is 320～360 ℃; The temperature of high temperature solid-state processing is 700～780 ℃ once more.
4. by the preparation method of the described use for safety type miner's lamp anode material for lithium-ion batteries of claim 1, it is characterized in that the protective atmosphere that high temperature solid-state is handled is N 2, Ar inert gas or Ar inert gas and H 2The mist of reducing gas, H 2Ratio be 5～10Vol%.
5. by the preparation method of the described use for safety type miner's lamp anode material for lithium-ion batteries of claim 1, it is characterized in that the heating rate when two sections high temperature solid-state are handled is 5～30 ℃/min.
6. by the preparation method of the described use for safety type miner's lamp anode material for lithium-ion batteries of claim 1, it is characterized in that the reaction time that two sections solid phases are handled was respectively 5～8 hours and 20～30 hours.
7. the described use for safety type miner's lamp lithium ion battery of claim 1 LiFePO 4The preparation method is characterized in that preparation-obtained LiFePO 4The particle diameter of powder is 1～2 μ m.
CNB200510110085XA 2005-11-07 2005-11-07 Anode material of lithium ion battery in use for safety type miner's lamp, and preparation method Expired - Fee Related CN100405638C (en)

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CN101314463B (en) * 2007-05-28 2011-04-06 上海比亚迪有限公司 Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode
US20100102270A1 (en) * 2007-05-28 2010-04-29 Wenwen Jia Method for Preparing Lithium Iron Phosphate as a Positive Electrode Active Material for a Lithium Ion Secondary Battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
中国稀土学报. 赖春艳、赵家昌、伏庆茂、解晶莹，177-179. 2004
中国稀土学报. 赖春艳、赵家昌、伏庆茂、解晶莹，177-179. 2004 *

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