CN105428594A - High-performance battery and preparation method - Google Patents
High-performance battery and preparation method Download PDFInfo
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- CN105428594A CN105428594A CN201510903297.7A CN201510903297A CN105428594A CN 105428594 A CN105428594 A CN 105428594A CN 201510903297 A CN201510903297 A CN 201510903297A CN 105428594 A CN105428594 A CN 105428594A
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- nitinol
- battery
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/04—Construction or manufacture in general
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a high-performance battery and a preparation method. The high-performance battery comprises a cathode, an anode, an electrolyte solution and a membrane for connecting the cathode and the anode, wherein the cathode is a composite piece composed of graphene and Ni-Ti alloy and consists of two layers, the Ni-Ti alloy is arranged on one layer, and the graphene is arranged on the other layer; the anode is Al-Si alloy, and the mass of Si accounts for 5-8% of the total mass of the Al-Si alloy; the electrolyte solution is a mixture composed of Al<3+>, Cl<-> and [EMIm]<+>, and the molar ratio of the [EMIm]<+> to the Al<3+> is greater than 3: 2 and smaller than 4: 1. The high-performance battery disclosed by the invention has relatively high heat stability, can overcome the safety problem of current lithium ion batteries, and cannot generate an explosion problem of the lithium ion secondary batteries; and moreover, the performance of the battery prepared in the invention is superior to that of reported high-performance batteries. The charging and discharging platform of the battery can reach more than 3.5 V, the cycle life can reach more than 5000 times, and the energy density of the battery can reach more than 90 Wh/Kg.
Description
Technical field
The present invention relates to heavy-duty battery and preparation method, belong to secondary cell field.
Background technology
Along with popularizing of movable equipment, lithium rechargeable battery has been widely used in the instruments such as various notebook computer, mobile phone.This is that energy density is high, discharge platform advantages of higher because lithium ion battery has.But, because liquid electrolyte needs to be packaged in the metal-back of sealing, when some improper use, easily there is accident.Such as, when battery works in high temperature environments, outside heat is delivered to inside battery by metal shell, or inside battery heat release when discharging current is larger, inside battery or outside are understood overheated and inner pressure of battery are increased considerably, and thus make battery explosion due to liquid electrolyte thermally labile.Therefore use the lithium rechargeable battery of liquid electrolyte to there is potential safety hazard, limit further developing of liquid electrolyte lithium rechargeable battery, current a lot of work all concentrates in the fail safe of raising secondary cell.
Patent CN104078679A has opened a kind of secondary aluminium cell, comprises positive pole, containing aluminum honeycomb and nonaqueous electrolytic solution.Described just very carbon nano tube/conducting sulfide polymer composite material.After being prepared into battery, its discharge voltage is 1.85V, and after 50 circulations, capacity attenuation is greater than 20%.
Chinese patent CN101937994A provides graphene/aluminum composite cathode material of a kind of lithium ion battery and preparation method thereof, and described negative material is 1: 0.1 ~ 100 to form by Graphene and aluminium in mass ratio, and capacity reaches 600 ~ 1200mAh/g.The battery invented is under the current density of 1-500mA/mg, and slaking is carried out in discharge and recharge 1-100 circulation, obtains silicon/carbon/graphite in lithium ion batteries alkene/aluminum honeycomb material after slaking.But the discharge platform of this battery is at below 1V, far below lithium rechargeable battery commercial at present.
Chinese patent CN103915611A discloses a kind of water system aluminium ion battery anode material and preparation method thereof, and this material is made up of nano titania leaf, and the chemical composition of nano titania leaf is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.Cycle-index can be brought up to 200 times by battery prepared by this invention, but its charging/discharging voltage is still lower, at below 2V, well below lithium rechargeable battery commercial at present.
Chinese patent CN103825045 discloses a kind of aluminium ion battery and preparation method thereof, and the just very transition group metallic oxide of this aluminium ion battery, negative pole are rafifinal; This invention improves the security performance of battery.But the discharge voltage of this battery is lower than 1 volt, also far below lithium rechargeable battery commercial at present, is therefore difficult to replace the application of current lithium rechargeable battery in the field such as mobile phone, electric motor car.
Chinese patent CN104241596A proposes a kind of rechargeable aluminium ion battery and preparation method thereof, and its positive pole adopts the material with carbon element of graphite-structure, and negative pole is rafifinal, and electrolyte is the mixture of anhydrous Aluminum chloride and 3-methylimidazole compounds.This invention adopts aluminium ion as conductive ion, avoids use lithium ion, has also evaded the conductivity issues because lithium ion causes thus.But the discharge platform of the battery of this invention is at below 2.4V, more much lower than the 4.2V of lithium ion battery, and its cycle-index is low.
The secondary aluminium cell that CN104183824A discloses a kind of secondary aluminium cell positive electrode and is made up of this positive pole.Described secondary aluminium cell comprises positive pole, containing aluminum honeycomb and nonaqueous electrolytic solution.Positive electrode is the composite material of Graphene/quinones, and wherein quinones is any one in quinone and corresponding derivative, and negative pole is metal aluminum or aluminum alloy, and electrolyte is that non-water is containing aluminium electrolyte.This battery adopts aluminium ion conduction, but its charging/discharging voltage is no more than 2V, and the capacity attenuation after 50 times that circulates is serious.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides a kind of heavy-duty battery and preparation method, adopts aluminium ion as conductive ion, gets rid of the elemental lithium existed in battery, can not produce the explosion issues of lithium rechargeable battery.
Technical scheme: for achieving the above object, heavy-duty battery of the present invention, comprises the barrier film of the described positive pole of positive pole, negative pole, electrolyte and connection and negative pole, the composite sheet that described just very Graphene and Nitinol are formed, be made up of two-layer, one deck is Nitinol, and another layer is Graphene; Described negative pole is alusil alloy, and wherein the quality of silicon accounts for the 5-8% of alusil alloy gross mass; Described electrolyte is for including Al
3+, Cl
-, [EMIm]
+the mixture formed, wherein [EMIm]
+with Al
3+mol ratio is greater than 3:2, is less than 4:1.
As preferably, the mass content sum total of other elements of described negative pole except aluminium silicon is less than 0.1%, and the thickness of alusil alloy is 0.2-2 millimeter.
As preferably, the thickness of described barrier film is 10-50 micron.
As preferably, the thickness of described Graphene is 50-2000 micron, and Nitinol thickness is 0.5-5 millimeter, and in Nitinol, the quality of nickel and titanium is half.
A preparation method for above-mentioned heavy-duty battery, comprises the following steps:
(1) thickness is the Nitinol of 0.5-5 millimeter is substrate, and adopt chemical vapour deposition technique on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 900 ~ 1000 DEG C, and the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet, as the positive pole of battery, controls sedimentary condition and makes the thickness of Graphene be 50-2000 micron;
(2) by [EMIm] Cl and AlCl
3mix by a certain percentage, obtain electrolyte, wherein [EMIm]
+with Al
3+mol ratio is greater than 3:2, is less than 4:1;
(3) arrange according to the order of Nitinol-Graphene composite sheet, barrier film, alusil alloy, wherein Nitinol-Graphene composite sheet is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, just obtaining heavy-duty battery.
Beneficial effect: heavy-duty battery of the present invention, there is higher thermal stability, can overcome the safety issue of current lithium ion battery, the explosion issues of lithium rechargeable battery can not be produced, and the battery prepared of the present invention is than the superior performance of the heavy-duty battery reported.The charge and discharge platform of this battery can reach more than 3.5V, and cycle life can reach more than 5000 times, and the energy density of battery can reach more than 90Wh/Kg.
Embodiment
Embodiment 1
(1) utilizing thickness to be the Nitinol of 0.5 millimeter is substrate, adopt chemical vapour deposition (CVD) (CVD) method on Nitinol, grow a layer graphene, deposition process utilizes that CH4 is carbon source, H2 is carrier gas, depositing temperature is 920 DEG C, deposit after 4 hours and lower the temperature, the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet thus, as the positive pole of battery, the thickness measuring Graphene is 228 microns;
(2) electrolyte is prepared: by [EMIm] Cl and AlCl
3mix in the ratio of 3:2;
(3) prepare PE barrier film, thickness is 18 microns;
(4) negative plate is prepared: its material is alusil alloy, and wherein the mass content of silicon is 8%, and thickness is 0.5 millimeter;
(5) order of above material according to Nitinol-Graphene composite sheet, barrier film, alusil alloy arranged, wherein Nitinol-Graphene is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery;
(6) battery testing: adopt Land electrochemical test system, tests the charge and discharge platform of this battery is 3.85V, and circulate after 8000 times, its capacitance loss 9%, the energy density of battery reaches 93Wh/Kg.
Embodiment 2
(1) utilizing thickness to be the Nitinol of 1.3 millimeters is substrate, and adopt chemical vapour deposition (CVD) (CVD) method on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 900 DEG C, and deposit after 8.6 hours and lower the temperature, the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet thus, and as the positive pole of battery, the thickness measuring Graphene is 1981 microns;
(2) electrolyte is prepared: by [EMIm] Cl and AlCl
3mix in the ratio of 2:1;
(3) prepare PE barrier film, thickness is 38 microns;
(4) negative plate is prepared: its material is alusil alloy, and wherein the mass content of silicon is 5.6%, and thickness is 0.2 millimeter;
(5) order of above material according to Nitinol-Graphene composite sheet, barrier film, alusil alloy arranged, wherein Nitinol-Graphene is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery;
(6) battery testing: adopt Land electrochemical test system, tests the charge and discharge platform of this battery is 3.8V, and circulate after 10000 times, its capacitance loss 8%, the energy density of battery reaches 97Wh/Kg.
Embodiment 3
1) utilizing thickness to be the Nitinol of 4 millimeters is substrate, and adopt chemical vapour deposition (CVD) (CVD) method on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 980 DEG C, and deposit after 2 hours and lower the temperature, the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet thus, and as the positive pole of battery, the thickness measuring Graphene is 111 microns;
(2) electrolyte is prepared: by [EMIm] Cl and AlCl
3mix in the ratio of 4:1;
(3) prepare PP/PE/PP barrier film, thickness is 20 microns;
(4) negative plate is prepared: its material is alusil alloy, and wherein the mass content of silicon is 7%, and thickness is 0.4 millimeter.
(5) order of above material according to Nitinol-Graphene composite sheet, barrier film, alusil alloy arranged, wherein Nitinol-Graphene is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery;
(6) battery testing: adopt Land electrochemical test system, tests the charge and discharge platform of this battery is 3.55V, and circulate after 8000 times, its capacitance loss 8%, the energy density of battery reaches 102Wh/Kg.
Embodiment 4
(1) utilizing thickness to be the Nitinol of 3.5 millimeters is substrate, and adopt chemical vapour deposition (CVD) (CVD) method on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 1000 DEG C, and deposit after 1 hour and lower the temperature, the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet thus, and as the positive pole of battery, the thickness measuring Graphene is 55 microns;
(2) electrolyte is prepared: by [EMIm] Cl and AlCl
3mix in the ratio of 5:2;
(3) prepare PP barrier film, thickness is 10 microns;
(4) negative plate is prepared: its material is alusil alloy, and wherein the mass content of silicon is 6%, and thickness is 0.2 millimeter;
(5) order of above material according to Nitinol-Graphene composite sheet, barrier film, alusil alloy arranged, wherein Nitinol-Graphene is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery;
(6) battery testing: adopt Land electrochemical test system, tests the charge and discharge platform of this battery is 3.95V, and circulate after 8000 times, its capacitance loss 6%, the energy density of battery reaches 94Wh/Kg.
Embodiment 5
(1) utilizing thickness to be the Nitinol of 5 millimeters is substrate, and adopt chemical vapour deposition (CVD) (CVD) method on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 900 DEG C, and deposit after 8.6 hours and lower the temperature, the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet thus, and as the positive pole of battery, the thickness measuring Graphene is 1977 microns;
(2) electrolyte is prepared: by [EMIm] Cl and AlCl
3mix in the ratio of 3:1;
(3) prepare PP/PE/PP barrier film, thickness is 50 microns;
(4) negative plate is prepared: its material is alusil alloy, and wherein the mass content of silicon is 5%, and thickness is 2 millimeters;
(5) order of above material according to Nitinol-Graphene composite sheet, barrier film, alusil alloy arranged, wherein Nitinol-Graphene is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery;
(6) battery testing: adopt Land electrochemical test system, tests the charge and discharge platform of this battery is 3.85V, and circulate after 8000 times, its capacitance loss 7%, the energy density of battery is 106Wh/Kg.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. a heavy-duty battery, is characterized in that: the barrier film comprising the described positive pole of positive pole, negative pole, electrolyte and connection and negative pole, and the composite sheet that described just very Graphene and Nitinol are formed is made up of two-layer, and one deck is Nitinol, and another layer is Graphene; Described negative pole is alusil alloy, and wherein the quality of silicon accounts for the 5-8% of alusil alloy gross mass; Described electrolyte is for including Al
3+, Cl
-, [EMIm]
+the mixture formed, wherein [EMIm]
+with Al
3+mol ratio is greater than 3:2, is less than 4:1.
2. heavy-duty battery according to claim 1, is characterized in that: the mass content sum total of other elements of described negative pole except aluminium silicon is less than 0.1%, and the thickness of alusil alloy is 0.2-2 millimeter.
3. heavy-duty battery according to claim 2, is characterized in that: the thickness of described barrier film is 10-50 micron.
4. heavy-duty battery according to claim 3, is characterized in that: the thickness of described Graphene is 50-2000 micron, and Nitinol thickness is 0.5-5 millimeter, and in Nitinol, the quality of nickel and titanium is half.
5. a preparation method for heavy-duty battery as claimed in claim 4, is characterized in that, comprises the following steps:
(1) thickness is the Nitinol of 0.5-5 millimeter is substrate, and adopt chemical vapour deposition technique on Nitinol, grow a layer graphene, deposition process utilizes CH
4for carbon source, H
2for carrier gas, depositing temperature is 900 ~ 1000 DEG C, and the speed of cooling is 15 DEG C/s, prepares Nitinol-Graphene composite sheet, as the positive pole of battery, controls sedimentary condition and makes the thickness of Graphene be 50-2000 micron;
(2) by [EMIm] Cl and AlCl
3mix by a certain percentage, obtain electrolyte, wherein [EMIm]
+with Al
3+mol ratio is greater than 3:2, is less than 4:1;
(3) arrange according to the order of Nitinol-Graphene composite sheet, barrier film, alusil alloy, wherein Nitinol-Graphene composite sheet is positive pole, and alusil alloy is negative pole, injects electrolyte and encapsulates, obtaining heavy-duty battery.
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|---|---|---|---|
| CN201510903297.7A CN105428594A (en) | 2015-12-09 | 2015-12-09 | High-performance battery and preparation method |
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|---|---|---|---|
| CN201510903297.7A CN105428594A (en) | 2015-12-09 | 2015-12-09 | High-performance battery and preparation method |
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ID=55506641
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5004654A (en) * | 1988-08-09 | 1991-04-02 | Alcan International Limited | Aluminium batteries |
| JP2001023650A (en) * | 1999-07-12 | 2001-01-26 | Tomoji Tanaka | Aluminum battery |
| CN1311538A (en) * | 2000-03-01 | 2001-09-05 | 东芝株式会社 | Aluminum battery |
| CN104269539A (en) * | 2014-09-30 | 2015-01-07 | 南京中储新能源有限公司 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
-
2015
- 2015-12-09 CN CN201510903297.7A patent/CN105428594A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5004654A (en) * | 1988-08-09 | 1991-04-02 | Alcan International Limited | Aluminium batteries |
| JP2001023650A (en) * | 1999-07-12 | 2001-01-26 | Tomoji Tanaka | Aluminum battery |
| CN1311538A (en) * | 2000-03-01 | 2001-09-05 | 东芝株式会社 | Aluminum battery |
| CN104269539A (en) * | 2014-09-30 | 2015-01-07 | 南京中储新能源有限公司 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
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Application publication date: 20160323 |