CN103606697A - Low-cost high-specific-capacity lithium ion battery - Google Patents
Low-cost high-specific-capacity lithium ion battery Download PDFInfo
- Publication number
- CN103606697A CN103606697A CN201310574508.8A CN201310574508A CN103606697A CN 103606697 A CN103606697 A CN 103606697A CN 201310574508 A CN201310574508 A CN 201310574508A CN 103606697 A CN103606697 A CN 103606697A
- Authority
- CN
- China
- Prior art keywords
- source
- ion battery
- lithium ion
- specific capacity
- low specific
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a low-cost high-specific-capacity lithium ion battery which comprises a positive pole piece, a negative pole piece, and a diaphragm and an electrolyte which are arranged between the positive pole piece and the negative pole piece; the negative pole comprises titanium dioxide, a lithium source, a dopant and a carbon source; and the molecular structural formula of the positive pole material is LixMnyFezM2-x-y-zO2. The negative pole material can greatly enhance the safety and cycle life of the lithium battery and lower the price of the lithium battery, and has the advantages of very low cost for the positive pole material, environment friendliness, high discharge specific capacity, favorable rate capability and favorable cycle stability.
Description
Technical field
The present invention relates to battery, be specifically related to the high lithium ion battery of the low specific capacity of a kind of cost.
Background technology
At present, in Chinese or global energy resource structure, coal, oil, natural gas primary energy account for more than 90%, and its reserves only supply exploitation about 50 years, and therefore developing new forms of energy must become the grand strategy industry of immuning from the economic downturn, create employment opportunities, seize future development commanding elevation.In the new forms of energy systems such as solar energy, wind energy, nuclear energy, lithium ion battery because its energy density is high, power density is high, good cycle, environmental friendliness, structure diversification and the excellent specific property such as cheap become the first-selected power supply of the walkie electronic apparatus such as video camera, mobile phone, notebook computer, are also the ideal sources of future space technology and high-end energy-storage system.
The actual discharge capacity of current commercial anode material for lithium-ion batteries is lower, can not meet the demand of electric automobile and hybrid power electric car.Lithium manganese oxide anode material is because of aboundresources, the low favor that enjoys researcher of cost, but spinel-type LiMn
2o
4actual discharge capacity and theoretical discharge capacity gap are larger, simultaneously because cyclical stability is poor and the shortcoming such as high temperature capacity attenuation has restricted its development to a certain extent.The LiMnO of layer structure
2difference between theoretical discharge capacity and actual discharge hold is larger, although can reach 190mAh/g, but because this material is difficult to synthesize, in cyclic process, battery structure, also in continuous variation, so need to find a kind of positive electrode, makes it have good reversible capacity, cycle performance and rate charge-discharge performance, and synthetic manufacturing process is simple, with low cost, batch good stability, to meet electrokinetic cell performance requirement.Lithium titanate is as a kind of novel negative material, and current potential, higher than 1.6 volts of carbon materials and lithium metals, therefore has good fail safe nearly.Meanwhile, lithium titanate anode material is in the embedding of lithium ion and deviate from process, and the structure of material is not impact almost, thus have " zero strain material " title, there is good cycle life.
Summary of the invention
The object of the invention is the defect for above-mentioned prior art, provide the low specific capacity of a kind of cost high lithium ion battery, have specific capacity high, high rate performance and good cycle, have extended cycle life, the advantage that cost price is low.
Object of the present invention can be achieved through the following technical solutions:
The lithium ion battery that the low specific capacity of cost is high, comprises positive plate, negative plate and is placed in barrier film and the electrolyte between positive and negative plate, described negative material comprises titanium dioxide, lithium source, dopant and carbon source, and the molecular structural formula of described positive electrode is Li
xmn
yfe
zm
2-x-y-zo
2.
The preparation of described negative material comprises the following steps:
A, titanium dioxide, lithium source, dopant and carbon source are mixed, add ethanol to make it moistening, be stirred to after pasty state mechanical ball milling 2～10 hours, ethanol is removed in vacuumize, pulverizes, and obtains presoma;
B, under protective gas atmosphere, presoma is placed at 300～500 ℃ to sintering 2～5 hours, obtain intermediate product, cooling and pulverize;
C, under protective gas atmosphere, the intermediate product after pulverizing is then placed at 600～900 ℃ to sintering 5～16 hours, make lithium ion battery negative material.
Described titanium dioxide is Detitanium-ore-type or brilliant red stone type nano titanium oxide.
Described lithium source is for the lithium oxalate containing the crystallization water with containing one or more mixing in the lithium nitrate of the crystallization water.
Described dopant is that one or more in oxide, nitrate, oxalates and the hydroxide of caesium, cerium, nickel, cobalt, silver mix, and carbon source is one or more mixing in ethanol, acrylic acid, glycolic and sucrose.
Li
xmn
yfe
zm
2-x-y-zo
2middle M is one or more of rare earth Sc, La, Pr, Nd, Pm, Sm, E μ, Gd, Tb, Dy, Ho, Er, Tm, Yb, L μ, 1≤a≤1.5,0 < b≤1,0 < c≤1.
The preparation of the material of described positive pole comprises the following steps:
A, take Li source, Mn source, Fe source, rare earth ion doped source and add in ball grinder, then add organic monomer and dispersant ball milling within 12～48 hours, to be mixed into uniform slurry;
B, slurry in add crosslinking agent, initator, catalyst, prepare gel, described crosslinking agent is N, a kind of in N` methylene-bisacrylamide, gelatin, 2wt%～10wt% that wherein addition of crosslinking agent is monomer mass, described initator is a kind of in ammonium persulfate, hydrogen peroxide, the addition of initator is the 1wt%～10wt% of organic monomer quality, described catalyst is tetraethylethylenediamine, the 1wt%～5wt% of the amount that the amount of catalyst is monomer;
C, gel is placed in to drying box, at 50 ℃～200 ℃, be dried, obtain xerogel, xerogel is placed in microwave oven, low fire, moderate heat or high fire are processed 10～60 minutes, be placed in again Muffle furnace, in oxygen enrichment or air atmosphere, in 500 ℃～900 ℃ sintering 3～12 hours, can obtain anode material for lithium-ion batteries of the present invention.
Organic monomer is a kind of in acrylamide, Methacrylamide, DMAA, acrylic acid, and wherein the addition of monomer is the 2wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass; Described dispersant is one or more in polyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, ammonium citrate, polyvinyl alcohol, and dispersant addition is the 1wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass.
Beneficial effect of the present invention: negative material of the present invention is made by double sintering, capacity is high, stable performance, quality has reached commerical grade requirement, can greatly improve fail safe and the cycle life of lithium battery, reduce its price, positive electrode forms take cheap manganese, iron as main, in addition rare earth doped on a small quantity, containing cobalt and nickel, therefore cost is very low, and environmental friendliness, the specific discharge capacity of material is high, high rate performance and good cycling stability, high temperature performance is compatible, can meet the performance requirement of power lithium-ion battery.
Embodiment
Below by embodiment, the present invention is described in detail.
Negative pole is by mixing lithium oxalate, nano titanium oxide, nitrate, sucrose containing the crystallization water.Above-mentioned raw materials is wetting with a small amount of ethanolic solution, fully stir, mix, add the amount of ethanol just to make raw material become pasty state, in the ball mill of 200r/min, ball milling is 5 hours, and the mixture after ball milling, through vacuumize, is then crushed and screened into presoma;
Presoma is placed in to nitrogen atmosphere, in tube furnace, calcines, with intelligent temperature control instrument, control temperature.In 3 hours, be heated to 400 ℃, be incubated 5 hours, cooling and pulverize after, then in 3 hours, be warming up to 700 ℃, be incubated 10 hours, naturally cool to room temperature, after grinding, obtain described Li
4ti
5o
12material.This material charge-discharge performance is stable, and specific capacity during 0.5C electric discharge can reach 160mAh/g.
Positive pole is weighed to above-mentioned four kinds of materials by product stoichiometric proportion and put into agate jar, the acrylamide that adds again material gross mass 10wt%, the polyethylene glycol of 3wt% and appropriate amount of deionized water, mixing and ball milling 40 hours, take out slurry, the N-N-methylene diacrylamine that adds while stirring monomer mass 5wt%, the ammonium persulfate solution of 2wt%, 1wt% tetramethylethylenediamine, continue to be stirred to generation jelly shape gel, after being put in 80 ℃ of drying boxes and drying, microwave moderate heat is processed 50min, 700 ℃ of constant temperature 10 hours in Muffle furnace under air atmosphere, cool to room temperature with the furnace, obtain Li
1.2mn
0.5fe
0.2nd
0.1o
2black powder.Products therefrom is rock salt structure, has higher phase purity.Particle is that porous class is spherical, and particle diameter is 600nm left and right.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technology people of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. the high lithium ion battery of the low specific capacity of cost, comprise positive plate, negative plate and be placed in barrier film and the electrolyte between positive and negative plate, it is characterized in that: described negative material comprises titanium dioxide, lithium source, dopant and carbon source, the molecular structural formula of described positive electrode is Li
xmn
yfe
zm
2-x-y-zo
2.
2. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 1, is characterized in that, the preparation of described negative material comprises the following steps:
A, titanium dioxide, lithium source, dopant and carbon source are mixed, add ethanol to make it moistening, be stirred to after pasty state mechanical ball milling 2～10 hours, ethanol is removed in vacuumize, pulverizes, and obtains presoma;
B, under protective gas atmosphere, presoma is placed at 300～500 ℃ to sintering 2～5 hours, obtain intermediate product, cooling and pulverize;
C, under protective gas atmosphere, the intermediate product after pulverizing is then placed at 600～900 ℃ to sintering 5～16 hours, make lithium ion battery negative material.
3. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 2, is characterized in that: described titanium dioxide is Detitanium-ore-type or brilliant red stone type nano titanium oxide.
4. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 2, is characterized in that: described lithium source is for the lithium oxalate containing the crystallization water with containing one or more mixing in the lithium nitrate of the crystallization water.
5. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 2, it is characterized in that: described dopant is that one or more in oxide, nitrate, oxalates and the hydroxide of caesium, cerium, nickel, cobalt, silver mix, and carbon source is one or more mixing in acrylic acid, glycolic and sucrose.
6. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 1, is characterized in that: Li
xmn
yfe
zm
2-x-y-zo
2middle M is one or more of rare earth Sc, La, Pr, Nd, Pm, Sm, E μ, Gd, Tb, Dy, Ho, Er, Tm, Yb, L μ, 1≤a≤1.5,0 < b≤1,0 < c≤1.
7. the high lithium ion battery of the low specific capacity of a kind of cost according to claim 6, is characterized in that, the preparation of the material of described positive pole comprises the following steps:
A, take Li source, Mn source, Fe source, rare earth ion doped source and add in ball grinder, then add organic monomer and dispersant ball milling within 12～48 hours, to be mixed into uniform slurry;
In B, slurry, add crosslinking agent, initator, catalyst, prepare gel, described crosslinking agent is a kind of in N-N-methylene diacrylamine, gelatin, 2wt%～10wt% that wherein addition of crosslinking agent is monomer mass, described initator is a kind of in ammonium persulfate, hydrogen peroxide, the addition of initator is the 1wt%～10wt% of organic monomer quality, and described catalyst is tetraethylethylenediamine, the 1wt%～5wt% of the amount that the amount of catalyst is monomer;
C, gel is placed in to drying box, at 50 ℃～200 ℃, be dried, obtain xerogel, xerogel is placed in microwave oven, low fire, moderate heat or high fire are processed 10～60 minutes, be placed in again Muffle furnace, in oxygen enrichment or air atmosphere, in 500 ℃～900 ℃ sintering 3～12 hours, can obtain anode material for lithium-ion batteries of the present invention.
8. according to the high lithium ion battery of the low specific capacity of a kind of cost described in 7 described in claim, it is characterized in that: organic monomer is a kind of in acrylamide, Methacrylamide, DMAA, acrylic acid, and wherein the addition of monomer is the 2wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass; Described dispersant is one or more in polyethylene glycol, ethanol, water, polyacrylic acid, ammonium polymethacrylate, ammonium citrate, polyvinyl alcohol, and dispersant addition is the 1wt～20wt% of Li source, Mn source, Fe source and rare earth ion doped source gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310574508.8A CN103606697A (en) | 2013-11-15 | 2013-11-15 | Low-cost high-specific-capacity lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310574508.8A CN103606697A (en) | 2013-11-15 | 2013-11-15 | Low-cost high-specific-capacity lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103606697A true CN103606697A (en) | 2014-02-26 |
Family
ID=50124910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310574508.8A Pending CN103606697A (en) | 2013-11-15 | 2013-11-15 | Low-cost high-specific-capacity lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103606697A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093704A (en) * | 2017-04-24 | 2017-08-25 | 浙江利城新能源有限公司 | A kind of preparation method of the lithium battery anode containing caesium |
| CN109742387A (en) * | 2019-01-16 | 2019-05-10 | 中国科学院福建物质结构研究所 | Rare earth doped lithium titanate electrode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101964415A (en) * | 2010-04-08 | 2011-02-02 | 浙江天能能源科技有限公司 | Method for preparing lithium-ion battery anode material |
| CN102088085A (en) * | 2010-12-29 | 2011-06-08 | 河南师范大学 | Lithium ion battery positive material and preparation method thereof |
-
2013
- 2013-11-15 CN CN201310574508.8A patent/CN103606697A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101964415A (en) * | 2010-04-08 | 2011-02-02 | 浙江天能能源科技有限公司 | Method for preparing lithium-ion battery anode material |
| CN102088085A (en) * | 2010-12-29 | 2011-06-08 | 河南师范大学 | Lithium ion battery positive material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093704A (en) * | 2017-04-24 | 2017-08-25 | 浙江利城新能源有限公司 | A kind of preparation method of the lithium battery anode containing caesium |
| CN109742387A (en) * | 2019-01-16 | 2019-05-10 | 中国科学院福建物质结构研究所 | Rare earth doped lithium titanate electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102088085B (en) | Lithium ion battery positive material and preparation method thereof | |
| CN101964415B (en) | Method for preparing lithium-ion battery anode material | |
| CN102760884A (en) | Cathode material for fast lithium ion conductor phase-modified lithium ion battery and preparation method thereof | |
| US20110114899A1 (en) | Nano-Positive Electrode Material of Lithium Cell and Method for Preparation thereof | |
| CN101964416A (en) | Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery | |
| CN102779993B (en) | Lithium ion battery anode material and preparation method | |
| WO2023124574A1 (en) | Titanium and zirconium co-doped, carbon-coated lithium iron phosphate material, preparation method therefor and use thereof | |
| CN103794773A (en) | Method for producing high-capacity 523-type ternary positive material | |
| CN103779559A (en) | Preparation method of lithium ion battery cathode material Li2Mn1-xMxSiO4/C | |
| CN103915627B (en) | Adopt high temperature insostatic pressing (HIP) method to prepare the method for ferrous silicate lithium anode material | |
| CN107742703A (en) | The method for preparing lithium ion battery lithium nickel cobalt aluminium composite oxide positive electrode | |
| CN102263263A (en) | Zinc and fluorine-doped carbon-coated lithium manganese phosphate cathode material and preparation method thereof | |
| CN105406038A (en) | High-capacity and high-cycle nanoscale lithium ferric manganese phosphate material synthesized by sol-gel method | |
| CN103682292B (en) | The lithium titanate material preparation method of high-tap density | |
| CN112151797A (en) | Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof | |
| CN102412393B (en) | Method and application of synthesis of Mg2V2O7 nanoparticles employing high temperature solid phase method | |
| CN102709548A (en) | Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material | |
| CN101908614B (en) | High-density lithium manganate anode material and preparation method thereof | |
| CN102185146B (en) | Rare-earth doped manganese-lithium phosphate anode material and preparation method thereof | |
| CN110323494A (en) | A kind of copper oxide helps the preparation method of burning lithium lanthanum zirconium oxygen solid electrolyte material | |
| CN103390746A (en) | Method for improving performance of lithium ion battery cathode material lithium titanate | |
| CN101944615B (en) | Lithium-manganese phosphate anode material for lithium ion battery and preparation method thereof | |
| CN101677125B (en) | Method for preparing layered cathode material of lithium ion battery | |
| CN101916860A (en) | Method for manufacturing electrochemical active material | |
| CN106410180A (en) | Lithium ion battery positive pole material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140226 |