CN106129331A - A kind of anode pole piece and the lithium titanate battery containing this anode pole piece - Google Patents
A kind of anode pole piece and the lithium titanate battery containing this anode pole piece Download PDFInfo
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- CN106129331A CN106129331A CN201610774141.8A CN201610774141A CN106129331A CN 106129331 A CN106129331 A CN 106129331A CN 201610774141 A CN201610774141 A CN 201610774141A CN 106129331 A CN106129331 A CN 106129331A
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- pole piece
- anode pole
- lithium
- transition metal
- lithium titanate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/485—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
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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
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- Crystallography & Structural Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to technical field of lithium batteries, it is specifically related to a kind of anode pole piece and the lithium titanate battery containing this anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive electrode material layer includes transition metal phosphate, transition metal phosphate has embedding lithium activity, and intercalation potential is 3 4.5V；A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned anode pole piece, and cathode pole piece is lithium titanate or modified lithium titanate.Active transition metal phosphate is added anode pole piece by the present invention, positive pole can be absorbed and enter irreversible lithium in negative pole, reduce the loss of positive pole lithium, thus improve lithium titanate battery efficiency first, and then raising battery capacity, and the operation of the method for the present invention is succinct, and with low cost, efficiency first and the capacity of lithium titanate battery can be improved, significant to the application development promoting lithium titanate battery.
Description
Technical field
The present invention relates to technical field of lithium batteries, be specifically related to a kind of anode pole piece and the metatitanic acid containing this anode pole piece
Lithium battery.
Background technology
Since 1991, what material with carbon element was creative applied to field of lithium ion battery, and brings this field revolutionary
Change, i.e. efficiently and after the repeatedly discharge and recharge of the carrying out of safety, it is just applied to mobile phone, video camera, notebook widely
On computer and other portable electronics.Compared with traditional plumbic acid, Ni-Cd, MH-Ni battery, lithium ion battery has higher
Specific volume energy density, weight/power ratio energy density, more preferable environment friendly, less self discharge and longer circulation longevity
Lives etc., are 21st century preferable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
The negative material of commercialization at present is mainly the graphite-like carbon materials such as native graphite, Delanium, MCMB
Material.Graphite-like material with carbon element, although have good conductivity, crystallization degree high, has advantages such as good charge and discharge platform, but due to
Graphite is layer structure, poor with organic solvent intermiscibility, in lithium ion battery charging process, its solvent molecule be easy to
Lithium ion embeds altogether and destroys graphite laminate structure in graphite flake layer, causes that graphite laminate structure is peeling-off, graphite granule is sent out
Life is burst apart or efflorescence, and then causes the deterioration of lithium ion battery cyclicity and the reduction of capacity；And due to the spy of graphite self structure
Different property, its high-power charge-discharge performance is the most relatively poor, therefore, limits graphite-like material with carbon element to a certain extent high-power
Application on lithium ion battery, this leaves the most wide development space also to non-graphite material with carbon element.
Lithium titanate (Li4Ti5O12) as a kind of lithium ion battery negative material, be compared to traditional graphite-like carbon and bear
Pole, has lot of advantages: cycle performance is excellent, and before and after lithium titanate charging, unit cell dimension is almost without change, is a kind of zero strain material
Material；Can fill soon, lithium titanate belongs to spinel structure, has the lithium ion tunnel of three-dimensional, and lithium ion diffusion velocity is fast；High safety,
The intercalation potential of lithium titanate is at about 1.55V, and far above Li dendrite deposition potential, without analysis lithium risk, lithium titanate is as one simultaneously
Planting transition metal oxide, its heat stability is far above graphite negative electrodes.Owing to lithium titanate has numerous advantages, therefore become
Focus in current Study on Li-ion batteries.
Lithium titanate efficiency first is the highest, up to more than 99%, and commercialization positive electrode such as LiCoO2, nickle cobalt lithium manganate,
Nickel cobalt lithium aluminate, LiFePO4、LiMn2O4The most inefficient, typically between 85%-95%.When so they form battery, titanium
The consumption of the irreversible lithium in acid lithium surface is little, but positive pole occupies lithium position owing to surface cenotype generates, partial structurtes are caved in, lithium/mistake
Cross the reasons such as metal mixing to cause lithium ion to be sloughed from structure can not returning；So, due to the irreversible lithium of positive pole not
Can go back to cause in lithium titanate, form dead lithium, thus result in lithium titanate battery inefficiency first, the problem that capacity is on the low side.
Therefore, the present invention provide a kind of can improve lithium titanate battery efficiency first and the anode pole piece of battery capacity and
Lithium titanate battery containing this anode pole piece.
Summary of the invention
It is an object of the invention to solve above technical problem, it is provided that a kind of anode pole piece and containing this anode pole piece
Lithium titanate battery, by phosphatic for active transition metal addition anode pole piece, can absorb positive pole and enter in negative pole irreversible
Lithium, reduces the loss of positive pole lithium, thus improves lithium titanate battery efficiency first, and then improve battery capacity.
For solve the problems referred to above, the present invention by the following technical solutions:
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, it is characterised in that
Described positive electrode material layer includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and intercalation potential is 3-4.5V.
Further, described transition metal phosphate is MPO4, wherein, M is activity trivalent transition metal ion.
Further, described M is Fe3+、Co3+、Ni3+、Mn3+、V3+In at least one.
Further, described transition metal phosphate also comprises doping metals, doping metals is Mg, Zn, Al, Ga, In,
In Cr, Zr, Ti, Nb, W at least one.
Further, described transition metal phosphate Surface coating conductive material, conductive material is carbon, CNT, stone
Ink alkene in any one.
Further, described transition metal phosphate has crystal structure or impalpable structure, is closed by chemical method
Become or electrochemistry takes off lithium synthesis.
Further, described positive electrode material layer also comprises active substance, conductive agent and binding agent.
Further, active substance in described positive electrode material layer: transition metal phosphate: conductive agent: the matter of binding agent
Amount ratio is 80-98:0.5-10:0.5-5:1-5.
Further, described active substance is LiCoO2, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiFePO4、
LiFeMnPO4、Li3V2(PO4)2、LiMn2O4In at least one
A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned anode pole piece, negative pole pole
Sheet is lithium titanate or modified lithium titanate.
The present invention is directed to the lithium titanate battery less than negative electrode active material of efficiency positive active material first: positive electrode active material
The reasons such as matter occupies lithium position when initial charge owing to surface cenotype generates, partial structurtes are caved in, lithium transition-metal mixing cause
Lithium ion is sloughed from structure and can not be returned, and the lithium that the higher efficiency first of negative pole lithium titanate makes positive pole come is substantially all
Enter embedding lithium position, but in lithium titanate, form dead lithium owing to the irreversible lithium of positive pole can not go back to cause, thus result in metatitanic acid
Lithium battery inefficiency first, the problem that capacity is on the low side.The phosphatic addition of active transition metal can absorb positive pole and enter negative
Irreversible lithium in extremely, reduces the loss of positive pole lithium, thus improves lithium titanate battery efficiency first, and then improve battery capacity.
A kind of anode pole piece of the present invention and the lithium titanate battery containing this anode pole piece, compared with prior art, it is dashed forward
The feature gone out and excellent effect are:
1. active transition metal phosphate is added anode pole piece by the present invention, can absorb positive pole and enter in negative pole irreversible
Lithium, reduces the loss of positive pole lithium, thus improves lithium titanate battery efficiency first, and then improve battery capacity.
2. the method operation of the present invention is succinct, with low cost, can improve efficiency first and the capacity of lithium titanate battery,
Significant to the application development promoting lithium titanate battery.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but this should be interpreted as the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements that knowledge and customary means are made or change, should be included in the scope of the present invention.
In below implementing, the intercalation potential of transition metal phosphate is between 3-4.5V.
Embodiment 1
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and described transition metal phosphate is FePO4,
Described positive electrode material layer also comprises active substance, conductive agent and binding agent, and active substance is LiFePO4, LiFePO4: FePO4: lead
Electricity agent: the mass ratio of binding agent is 80:10:5:5；A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described just
Pole pole piece is above-mentioned anode pole piece, and cathode pole piece is modified lithium titanate.
Embodiment 2
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and intercalation potential is 4V, described transition metal phosphorus
Hydrochlorate is MnPO4Described MnPO4 also comprises doping metals, and doping metals is Mg, described positive electrode material layer also comprise active substance,
Conductive agent and binding agent, active substance is LiCoO2, LiCoO2: MnPO4: conductive agent: the mass ratio of binding agent is 98:0.5:
0.5:1；A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned anode pole piece, negative
Pole pole piece is lithium titanate.
Embodiment 3
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and described transition metal phosphate is CoPO4,
Described transition metal phosphate Surface coating conductive material, described conductive material is carbon；State positive electrode material layer and also comprise active matter
Matter, conductive agent and binding agent, active substance is nickle cobalt lithium manganate, nickle cobalt lithium manganate: CoPO4: conductive agent: the mass ratio of binding agent
For 88:7:3:2；A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned positive pole pole
Sheet, cathode pole piece is modified lithium titanate.
Embodiment 4
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and described transition metal phosphate is VPO4, institute
Stating transition metal phosphate and also comprise doping metals, doping metals is Al and W, and described transition metal phosphate Surface coating conducts electricity
Material carbon nanotube, described transition metal phosphate has crystal structure, and by being chemically synthesized, described positive electrode material layer is also
Comprise active substance, conductive agent and binding agent, active substance in described positive electrode material layer: VPO4: conductive agent: the quality of binding agent
Ratio is 90:5:3:2, and described active substance is nickle cobalt lithium manganate and LiMn2O4Mixture；A kind of lithium titanate battery, including just
Pole pole piece and cathode pole piece, described anode pole piece is above-mentioned anode pole piece, and cathode pole piece is modified lithium titanate.
Embodiment 5
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and intercalation potential is 4V, described transition metal phosphorus
Hydrochlorate is MPO4, wherein, M is activity trivalent transition metal ion, and described M is Fe3+And Mn3+, described transition metal phosphate table
Bread covers conductive material Graphene, described positive electrode material layer also comprises active substance, conductive agent and binding agent, described positive pole material
Active substance in the bed of material: transition metal phosphate: conductive agent: the mass ratio of binding agent is 86:7:4:3, described active substance is
Nickel cobalt lithium aluminate and LiMn2O4；A kind of lithium titanate battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned
Anode pole piece, cathode pole piece is lithium titanate.
Embodiment 6
A kind of anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, described positive pole material
The bed of material includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and described transition metal phosphate is MPO4, its
In, M is activity trivalent transition metal ion, and described M is Fe3+, described transition metal phosphate also comprises doping metals, doping gold
Belonging to Al, described transition metal phosphate Surface coating conductive material carbon, described transition metal phosphate has crystal structure, passes through
Electrochemistry takes off lithium synthesis, and described positive electrode material layer also comprises active substance, conductive agent and binding agent, lives in described positive electrode material layer
Property material: FePO4: conductive agent: the mass ratio of binding agent is 85:5:5:5, described active substance is Li3V2(PO4)2；A kind of titanium
Acid lithium battery, including anode pole piece and cathode pole piece, described anode pole piece is above-mentioned anode pole piece, and cathode pole piece is Modified Titanium
Acid lithium.
Claims (10)
1. an anode pole piece, including plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface, its feature exists
In, described positive electrode material layer includes that transition metal phosphate, transition metal phosphate have embedding lithium activity, and intercalation potential is 3-
4.5V。
A kind of anode pole piece the most according to claim 1, it is characterised in that described transition metal phosphate is MPO4, its
In, M is activity trivalent transition metal ion.
A kind of anode pole piece the most according to claim 2, it is characterised in that described M is Fe3+、Co3+、Ni3+、Mn3+、V3+In
At least one.
A kind of anode pole piece the most according to claim 2, it is characterised in that described transition metal phosphate also comprises doping
Metal, doping metals is at least one in Mg, Zn, Al, Ga, In, Cr, Zr, Ti, Nb, W.
5. according to a kind of anode pole piece described in claim 1-4 any one, it is characterised in that described transition metal phosphate
Surface coating conductive material, conductive material is any one in carbon, CNT, Graphene.
A kind of anode pole piece the most according to claim 1, it is characterised in that described transition metal phosphate has crystal knot
Structure or impalpable structure, by be chemically synthesized or electrochemistry take off lithium synthesize.
A kind of anode pole piece the most according to claim 1, it is characterised in that described positive electrode material layer also comprises active matter
Matter, conductive agent and binding agent.
A kind of anode pole piece the most according to claim 7, it is characterised in that active substance in described positive electrode material layer: vanadium
Acid lithium: conductive agent: the mass ratio of binding agent is 80-98:0.5-10:0.5-5:1-5.
9. according to a kind of anode pole piece described in claim 7 or 8, it is characterised in that described active substance is LiCoO2, nickel cobalt
LiMn2O4, nickel cobalt lithium aluminate, LiFePO4、LiFeMnPO4、Li3V2(PO4)2、LiMn2O4In at least one.
10. a lithium titanate battery, including anode pole piece and cathode pole piece, it is characterised in that described anode pole piece is that right is wanted
Seeking the anode pole piece described in 1-9 any one, cathode pole piece is lithium titanate or modified lithium titanate.
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| CN201610774141.8A CN106129331A (en) | 2016-08-31 | 2016-08-31 | A kind of anode pole piece and the lithium titanate battery containing this anode pole piece |
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| CN201610774141.8A CN106129331A (en) | 2016-08-31 | 2016-08-31 | A kind of anode pole piece and the lithium titanate battery containing this anode pole piece |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878955A (en) * | 2018-04-11 | 2018-11-23 | 浙江湖州中科新伏能源科技有限公司 | A kind of graphene lithium titanate battery |
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| CN102332563A (en) * | 2010-12-17 | 2012-01-25 | 东莞新能源科技有限公司 | Preparation method for anode material of lithium ion battery |
| CN101378897B (en) * | 2006-02-01 | 2013-03-27 | 加拿大魁北克电力公司 | Multilayer material, method for making same and use as electrode |
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2016
- 2016-08-31 CN CN201610774141.8A patent/CN106129331A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378897B (en) * | 2006-02-01 | 2013-03-27 | 加拿大魁北克电力公司 | Multilayer material, method for making same and use as electrode |
| CN101841039A (en) * | 2010-04-29 | 2010-09-22 | 上海电力学院 | Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof |
| CN102332563A (en) * | 2010-12-17 | 2012-01-25 | 东莞新能源科技有限公司 | Preparation method for anode material of lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878955A (en) * | 2018-04-11 | 2018-11-23 | 浙江湖州中科新伏能源科技有限公司 | A kind of graphene lithium titanate battery |
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Application publication date: 20161116 |