CN105895912A - High-voltage lithium ion battery - Google Patents
High-voltage lithium ion battery Download PDFInfo
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- CN105895912A CN105895912A CN201610277884.4A CN201610277884A CN105895912A CN 105895912 A CN105895912 A CN 105895912A CN 201610277884 A CN201610277884 A CN 201610277884A CN 105895912 A CN105895912 A CN 105895912A
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- Prior art keywords
- carbon
- oxide
- metal
- complex
- cobalt phosphate
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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
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-voltage lithium ion battery. The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein lithium cobalt phosphate and a compound thereof are used as the positive electrode active material; the lithium cobalt phosphate and the compound thereof are at least selected from lithium cobalt phosphate and a carbon compound thereof, lithium cobalt phosphate and a metal ion doped compound thereof, and lithium cobalt phosphate and a conductive polymer compound thereof. Compared with the prior art, the metal oxide negative electrode and lithium cobalt phosphate positive electrode based high-voltage lithium ion battery provided by the invention has the characteristics of high safety, high specific capacity, and high specific energy; and the lithium cobalt phosphate positive electrode material has the characteristics of high voltage, high safety and high structural stability, so that the lithium cobalt phosphate positive electrode material is expected to be a new generation of a 5V high-voltage, high-capacity and high-energy-density positive electrode material.
Description
Technical field
The invention belongs to electrochemical field, be specifically related to a kind of Novel high voltage lithium ion battery.
Background technology
Therefore the 21 century mankind must tap a new source of energy in the face of the energy and two Tough questions of environment and renewable and clean energy resource has
Profound significance.Electric automobile uses the Fossil fuels such as electric energy replacement oil as power, has the advantage of energy-conserving and environment-protective, is subject to
Arrive the concern in the whole world.In the study hotspot relevant to electric automobile, battery technology is considered topmost difficulty.But mesh
Front power ion battery systems, at specific energy, specific power, service life, one-tenth present aspect, there is also the most urgently to be resolved hurrily asking
Topic.Therefore, design safety is good, specific energy density is high, the power lithium-ion battery of cycle performance length is necessary and urgent in exploitation
's.
Anode material for lithium-ion batteries is one of important component part of lithium ion battery, and its research and development directly influences lithium ion
Battery overall performance.LiCoPO4Crystal has the structure that olivine-type orderly as LiFePO4 is stable, belongs to orthorhombic
System, theoretical discharge capacity is 167mAh/g, LiCoPO4It is good that positive electrode has security performance, high relative to lithium electrode electromotive force (about
4.8V), it is expected to become a new generation high power capacity, high voltage, the positive electrode of high-energy-density.
Additionally, negative material is also to improve lithium ion battery energy and the key factor of cycle life.At present, commercially use
Negative material is mostly graphite cathode material.Such negative material has good charge and discharge platform and a structural stability, but in fact
Border specific discharge capacity (about 330 MAhs/g), close to its theoretical value (372 MAhs/g), cannot meet a new generation's lithium ion
The demand of battery.Therefore, the negative material developing, designing novel high-capacity is extremely urgent.In the process finding graphite substitute
In, some transition metal oxides such as Fe2O3、Fe3O4、Co3O4, CoO, NiO, CuO, ZnO etc. higher because having
Theoretical capacity (600～1200 MAhs/g), environmental friendliness, safety are good, low cost and other advantages, become lithium ion secondary electricity
The study hotspot of pond negative material.
Therefore, with LiCoPO4As positive electrode, using metal-oxide negative pole as negative material, designing, studying, opening
Send out Novel high voltage, high security, the cobalt phosphate lithium/metal-oxide power lithium-ion battery of high-energy-density have important science
Meaning and commercial application are worth.
Summary of the invention
It is an object of the invention to provide a kind of novel high-voltage lithium ion batteries.
The present invention provides a kind of high-voltage lithium ion batteries, and described lithium ion battery comprises positive pole, negative pole, barrier film and electrolyte,
Using cobalt phosphate lithium and complex thereof as positive active material.Cobalt phosphate lithium and complex thereof are at least selected from: cobalt phosphate lithium and
Its carbon complex, cobalt phosphate lithium and metal ion mixing complex, cobalt phosphate lithium and conductive polymer composite thereof.
Carbon in described cobalt phosphate lithium and carbon complex thereof is porous, electrically conductive carbon black (Ketjenblack EC600JD), micropore superconduction
Carbon black (BP2000), carbon nano-fiber (CNFs), ordered mesopore carbon (OMC), porous carbon (CMK-3), graphene oxide (GO),
Graphene (Graphene) etc. has the one in the material with carbon element of high-specific surface area and superior electrical conductivity energy.
Using metal-oxide and carbon composite thereof as negative electrode active material.Metal-oxide and carbon-based composite thereof are at least selected from:
Iron oxides and carbon-based composite thereof, Mn oxide and carbon-based composite thereof, cobalt/cobalt oxide and carbon-based composite thereof, nickel oxide
And carbon-based composite, Cu oxide and carbon-based composite thereof and zinc oxide and carbon-based composite thereof.
Described iron oxides is FeO, Fe3O4、Fe2O3One or more；The oxide of described manganese is MnO, Mn3O4、
Mn2O3One or more；Described cobalt/cobalt oxide is CoO, Co3O4One or more；Described nickel oxide is NiO；
Described Cu oxide is CuO, Cu2One or more of O；Described zinc oxide is ZnO.
Described metal-oxide and carbon-based composite thereof at least include: metal-oxide/porous carbon complex, metal-oxide/
Carbon mano-tube composite, metal-oxide/graphene complex, metal-oxide/carbon black complex, metal-oxide/graphite is multiple
Compound, metal-oxide/carbonaceous mesophase spherules complex.Porous carbon be selected from containing in macropore, mesoporous, micropore at least one
Material with carbon element.One or more in acetylene black, Ketjen black of carbon black.Graphite is selected from native graphite, electrographite, modified stone
One or more in ink.
The present invention provides a kind of method preparing described high-voltage lithium ion batteries, by containing metal-oxide negative electrode active material
Electrode, as negative pole, matches with cobalt phosphate lithium and complex positive pole thereof.
One energy storage elements of the present invention, described energy storage elements contains described lithium ion battery.
Beneficial effect:
Compared with prior art, high-voltage lithium ion based on metal-oxide negative pole and the cobalt phosphate lithium positive pole electricity that the present invention provides
Pond, has the advantages that safety is good, specific capacity is high, specific energy is high.Cobalt phosphate lithium positive electrode have high voltage, high security,
The feature of high structural stability, is expected to become a new generation 5V high voltage, high power capacity, the positive electrode of high-energy-density.
It addition, metal-oxide negative pole relative to the voltage platform of lithium metal between 0.5～2.1V, its surface does not has lithium metal to analyse
Going out, safety is good；And, the metal ion in metal-oxide negative material occurs based on electron rich oxidation also with lithium ion
Former reaction, theoretical specific capacity is the highest can reach 1200 MAhs/g.Theoretical capacity according to full battery calculates, it is found that
When positive electrode capacity keeps constant, and capacity of negative plates is when 1000-1200 MAh/g, and the specific capacity of full battery just can obtain the biggest
The lifting of degree, the use of high power capacity metal-oxide negative pole improves the energy density of full battery.Additionally, metal-oxide is born
Pole material source enriches, and low price has potential using value.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve of the lithium ion battery of embodiment 1.
Fig. 2 is the charging and discharging curve of the lithium ion battery of embodiment 2.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as without special
Different explanation, the most commercially obtains.
Embodiment 1, LiCoPO4The assembling of/carbon positive pole full the battery of-MnO/ Carbon anode and electrochemical property test thereof
(1) preparation of positive pole
By LiCoPO4/ carbon: carbon black: binding agent=(7～9): (0.5～2): ratio (mass ratio) mixing of (0.5～1),
After mix homogeneously, be coated on aluminum collector, vacuum dried, section after, obtain anode pole piece.Described carbon is porous, electrically conductive
Carbon black (Ketjenblack EC600JD), micropore superconduction carbon black (BP2000), carbon nano-fiber (CNFs), ordered mesopore carbon (OMC),
Porous carbon (CMK-3), graphene oxide (GO), Graphene (Graphene) etc. have high-specific surface area and the carbon of superior electrical conductivity energy
One in material.
(2) preparation of negative pole
According to MnO/ carbon complex: carbon black: binding agent=(7～9): (0.5～2): the ratio (mass ratio) of (0.5～1) is mixed
Close, after mix homogeneously, be coated on copper current collector, vacuum dried, section after, obtain cathode pole piece.MnO/ carbon complex
Middle material with carbon element is porous charcoal.
(3) assembling of full battery
Between a positive electrode and a negative electrode insert microporous polypropylene membrane Celgard2300 (celgard barrier film company limited of the U.S.) as every
Film, adds carbonic ester electrolyte [1M LiPF6The DMC (dimethyl carbonate) of (lithium hexafluoro phosphate)/EC (vinyl carbonate)/PC (carbon
Acid propylene ester) (volume ratio is 1:1:1) solution].
(4) test of full battery
The full battery of above-mentioned assembling is carried out on charge-discharge test instrument charge-discharge test, and the discharge and recharge interval of test is 2.0 4.2V.
Test temperature is 25 DEG C, and battery capacity and charging and discharging currents are based on the quality of positive electrode and calculate.Fig. 1 be described based on
LiCoPO4The full battery of/carbon positive pole-MnO/ carbon charging and discharging curve under the conditions of 0.1C, first discharge specific capacity can reach
161mA h/g。
Embodiment 2, LiCoPO4/ carbon positive pole-Fe3O4The assembling of the full battery of/Carbon anode and electrochemical property test thereof
(1) preparation of positive pole
By LiCoPO4/ carbon: carbon black: binding agent=(7～9): (0.5～2): ratio (mass ratio) mixing of (0.5～1),
After mix homogeneously, be coated on aluminum collector, vacuum dried, section after, obtain anode pole piece.Described carbon is porous, electrically conductive
Carbon black (Ketjenblack EC600JD), micropore superconduction carbon black (BP2000), carbon nano-fiber (CNFs), ordered mesopore carbon (OMC),
Porous carbon (CMK-3), graphene oxide (GO), Graphene (Graphene) etc. have high-specific surface area and the carbon of superior electrical conductivity energy
One in material.
(2) preparation of negative pole
According to Fe3O4/ carbon: carbon black: binding agent=(7～9): (0.5～2): ratio (mass ratio) mixing of (0.5～1), mixed
After closing uniformly, it is coated on copper current collector, after vacuum dried, section, obtains cathode pole piece.Fe3O4Carbon in/carbon complex
Material is porous charcoal.
(3) assembling of full battery
Between a positive electrode and a negative electrode insert microporous polypropylene membrane Celgard2300 (celgard barrier film company limited of the U.S.) as every
Film, adds carbonic ester electrolyte [1M LiPF6The DMC (dimethyl carbonate) of (lithium hexafluoro phosphate)/EC (vinyl carbonate)/PC (carbon
Acid propylene ester) (volume ratio is 1:1:1) solution].
(4) test of full battery
The full battery of above-mentioned assembling is carried out on charge-discharge test instrument charge-discharge test, and the discharge and recharge interval of test is 2.0～4.2V.
Test temperature is 25 DEG C, and battery capacity and charging and discharging currents are based on the quality of positive electrode and calculate.Fig. 2 be described based on
LiCoPO4/ carbon positive pole-Fe3O4/ Carbon anode full battery charging and discharging curve under the conditions of 0.1C, specific discharge capacity reaches 120mA
h/g。
In sum, what the present invention provided has high voltage, high security, high structural stability based on cobalt phosphate lithium positive electrode
Feature, be expected to become a new generation 5V high voltage, high power capacity, the positive electrode of high-energy-density.The tool of metal-oxide negative pole
Having higher specific capacity and excellent cyclical stability, and the raw material of metal-oxide negative pole is easy to get, cost is relatively low, thus this
Cobalt phosphate lithium-metal-oxide/the carbon battery of invention is expected to as a kind of energy storage device that novel safety is good and energy density is high,
Have a good application prospect.Foregoing is only the preferred embodiments of the present invention, is not intended to limit embodiment of the present invention,
Those of ordinary skill in the art, according to the central scope of the present invention and spirit, can carry out corresponding flexible or amendment very easily,
Therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (6)
1. a high-voltage lithium ion batteries, described lithium ion battery comprises positive pole, negative pole, barrier film and electrolyte, and its feature exists
In:
At least be selected from using cobalt phosphate lithium and complex thereof as positive active material, cobalt phosphate lithium and complex thereof: cobalt phosphate lithium and
Its carbon complex, cobalt phosphate lithium and metal ion mixing complex, cobalt phosphate lithium and conductive polymer composite thereof.
A kind of high-voltage lithium ion batteries the most according to claim 1, it is characterised in that described cobalt phosphate lithium and carbon thereof
Carbon in complex is porous, electrically conductive carbon black, micropore superconduction carbon black, carbon nano-fiber, ordered mesopore carbon, porous carbon, oxidation stone
Ink alkene, Graphene etc. have the one in the material with carbon element of high-specific surface area and superior electrical conductivity energy.
A kind of high-voltage lithium ion batteries the most according to claim 1, it is characterised in that multiple with metal-oxide and carbon thereof
Condensation material is at least selected from as negative electrode active material, metal-oxide and carbon-based composite thereof: iron oxides and carbon-based composite thereof,
Mn oxide and carbon-based composite thereof, cobalt/cobalt oxide and carbon-based composite thereof, nickel oxide and carbon-based composite thereof, Cu oxide
And carbon-based composite and zinc oxide and carbon-based composite thereof；
Described iron oxides is FeO, Fe3O4、Fe2O3One or more；The oxide of described manganese is MnO, Mn3O4、
Mn2O3One or more；Described cobalt/cobalt oxide is CoO, Co3O4One or more；Described nickel oxide is NiO；
Described Cu oxide is CuO, Cu2One or more of O；Described zinc oxide is ZnO.
A kind of high-voltage lithium ion batteries the most according to claim 1, it is characterised in that described metal-oxide and
Carbon-based composite at least includes: metal-oxide/porous carbon complex, metal oxide/carbon nano-tube complex, metal-oxide
/ graphene complex, metal-oxide/carbon black complex, metal-oxide/graphite composite, metal-oxide/mesocarbon is micro-
Ball complex；Porous carbon is selected from containing the material with carbon element of at least one in macropore, mesoporous, micropore；Carbon black is selected from acetylene black, section
One or more during qin is black；One or more in native graphite, electrographite, modified graphite of graphite.
5. the method for the high-voltage lithium ion batteries prepared as described in Claims 1 to 5, it is characterised in that described method is
Using the electrode containing metal-oxide negative electrode active material as negative pole, match with cobalt phosphate lithium and complex positive pole thereof.
6. an energy storage elements, it is characterised in that described energy storage elements contains the lithium ion described in Claims 1 to 5
Battery.
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| CN201610277884.4A CN105895912A (en) | 2016-04-28 | 2016-04-28 | High-voltage lithium ion battery |
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| CN201610277884.4A CN105895912A (en) | 2016-04-28 | 2016-04-28 | High-voltage lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221699A (en) * | 2017-05-27 | 2017-09-29 | 江苏大学 | A kind of novel high voltage lithium ion battery and energy storage elements based on silicium cathode |
| CN109659560A (en) * | 2018-12-26 | 2019-04-19 | 赵宏伟 | A kind of cobalt phosphate lithium positive electrode and preparation method for lithium ion battery |
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Application publication date: 20160824 |