WO2014012379A1 - Self-charging lithium-ion battery - Google Patents
Self-charging lithium-ion battery Download PDFInfo
- Publication number
- WO2014012379A1 WO2014012379A1 PCT/CN2013/072685 CN2013072685W WO2014012379A1 WO 2014012379 A1 WO2014012379 A1 WO 2014012379A1 CN 2013072685 W CN2013072685 W CN 2013072685W WO 2014012379 A1 WO2014012379 A1 WO 2014012379A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- current collector
- material layer
- electrode material
- ion battery
- self
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002070 nanowire Substances 0.000 claims abstract description 98
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000007774 positive electrode material Substances 0.000 claims abstract description 45
- 239000007773 negative electrode material Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000003491 array Methods 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 238000009413 insulation Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- -1 polyparaphenylene Polymers 0.000 claims description 16
- 239000011149 active material Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- RRKXGHIWLJDUIU-UHFFFAOYSA-N 5-bromo-8-chloroisoquinoline Chemical compound C1=NC=C2C(Cl)=CC=C(Br)C2=C1 RRKXGHIWLJDUIU-UHFFFAOYSA-N 0.000 claims description 2
- 241000283070 Equus zebra Species 0.000 claims description 2
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/46—Accumulators structurally combined with charging apparatus
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
-
- 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
Definitions
- the present invention relates to a lithium ion battery, and more particularly to a self-charging lithium ion battery capable of simultaneously harvesting energy and storing electric charge. Background technique
- Lithium-ion battery is a kind of rechargeable battery, which is widely used in daily life because of its convenient application and portability.
- Lithium-ion batteries are developed from lithium batteries, which consist of a positive electrode, an electrolyte, a negative electrode, and a polymer separator.
- the positive electrode material usually employs a compound containing lithium ions, such as lithium manganate, lithium cobaltate, lithium nickel cobalt manganese oxide, or the like.
- the polymer membrane is usually provided with a microporous structure, allowing lithium ions to pass freely, and electrons cannot pass.
- the working principle of the lithium ion battery is as follows: When charging, Li + is deintercalated from the positive electrode, and the electrolyte is inserted into the negative electrode, and the negative electrode is in a lithium-rich state; when discharging, Li + is deintercalated from the negative electrode and returns to the positive electrode through the electrolyte.
- Traditional lithium-ion batteries rely on an external power source to complete their own charging. The battery is just a charge storage device.
- lithium-ion batteries are one of their most important power sources. Charging a Li-Ion battery usually requires an external power supply to provide a constant current or voltage. Therefore, in the case of some shortcomings such as a trip, a power outage, and the like, there is a possibility that the charging of the lithium ion battery may be difficult, which may cause inconvenience to people.
- the technical problem to be solved by the invention is: overcome the defect that the existing lithium ion battery needs external power supply charging, and provide a self-charging lithium ion battery, which can apply the electric field generated by the nano generator to complete the charging of the lithium ion battery, and is convenient to use, especially Suitable for applications where external power is scarce.
- the first technical solution provided by the present invention is a self-charging lithium ion battery, comprising a first current collector 1, a piezoelectric nanowire array 2, a second current collector 3, a positive electrode material layer 4, and a polymerization.
- the materials used in the first current collector and the second current collector are independently selected from the group consisting of aluminum, copper, nickel, polyaniline, polyacetylene, polypyrrole, polythiophene, polyparaphenylene Or polyphenylacetylene.
- the active material used in the positive electrode material layer is lithium manganate, lithium iron phosphate, lithium cobaltate or Li-Ni-Co-Mn-0 ternary positive electrode material.
- the negative electrode receives lithium ions during charging, and the positive electrode releases lithium ions; while in the discharge process, the negative electrode releases lithium ions, and the positive electrode receives lithium ions.
- the positive and negative electrodes of a lithium ion battery typically include a current collector and a layer of material disposed on the current collector.
- the present invention has no special requirements for the materials used for the polymer separator.
- Conventional polymer separators for lithium ion batteries can be applied to the present invention, such as a single-layer polypropylene microporous membrane (PP), a single-layer polyethylene microporous membrane (PE), Multilayer polypropylene microporous membrane, multilayer polyethylene microporous membrane, etc.
- the overall size of the self-charging lithium ion battery of this embodiment is 40 x 60 mm.
- An aluminum foil having a purity of 99.5% thick ⁇ was used as the first current collector 1 , and an RF sputtering copper layer of ⁇ was used as the second current collector 3.
- a plurality of oxidized nanowire arrays 2 are grown on the first current collector 1, and the length of the oxidized nanowires is 20 ⁇ m.
- the photoresist material is equivalent to a zoned mold during the subsequent oxidation of the nanowires, so that the oxidized nanowires are only grown in the region where the exposed oxidized seeds are present, thereby realizing the presence of voids between the oxidized nanowire arrays 2.
- the specific oxidation method of the nanowires is as follows: 0.1 mol/L concentration consisting of equimolar cyclohexamethylenetetramine (HMTA) and nitric acid hexahydrate (ZnN0 3 .6 (H 2 0) )
- the culture solution was prepared by placing the aluminum foil with the oxidized seed layer face down on the top of the culture solution and growing at 85 ° C for 20 hours in a mechanical convection oven (Model: Yamato DKN400, Santa Clara, Calif.) .
- the aluminum foil grown with the oxidized nanowires was rinsed with deionized water and dried in air. All remaining photoresist material was then peeled off and the nanowire array was annealed at 150 °C.
- a polymer insulating layer polydecyl acrylate layer
- Lithium cobaltate (average particle diameter 10 ⁇ ⁇ ), acetylene black, and polytetrafluoroethylene material were mixed at a mass ratio of 85:10:5, and then the above mixture was mixed with hydrazine (mercaptopyrrolidone) to obtain a solid content of 20 % of the slurry for the positive electrode material layer.
- the slurry was uniformly coated in the separation gap of the piezoelectric nanowire array 2 on the surface of the first current collector 1 in accordance with the dry mass of the material layer of 15 mg/cm 2 . Next, it was dried at 50 ° C for 5 minutes to form a positive electrode material layer 4 .
- the polymer separator 5 is placed spaced apart from the positive electrode material layer 4.
- Graphite (average particle diameter: 20 ⁇ m) and ethanol were mixed to obtain a slurry for a negative electrode material layer having a solid content of 20% by mass.
- the anode material layer slurry is applied in the separation gap of the piezoelectric nanowire array 2 with respect to the polymer separator.
- the coating amount of the slurry was such that the dry mass of the material layer reached 15 mg/cm 2 .
- the mixture was dried at a temperature of 50 ° C for 15 minutes, and the solvent was removed to obtain a negative electrode material layer 6.
- An electrolyte (a solution of ethylene carbonate in which LiPF 6 is dissolved at a concentration of 1 mol/L) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6 (not shown), and then utilized.
- RF sputtering The copper layer (second current collector) 3 was placed on the polymer insulating layer 7 and the negative electrode material layer 6, and then encapsulated with an epoxy resin to obtain a self-charging lithium ion battery sample 1#.
- the sample 1# was placed in an ultrasonic wave of 1 Hz for 2 minutes, and after taking out, a discharge test was performed, and a constant current discharge was performed at 0.02 mA, and the discharge capacity of the sample 1# was 2.3 mAh.
- the overall size of the self-charging lithium ion battery of this embodiment is 40 x 60 mm.
- An aluminum foil having a purity of 99.5% thick ⁇ was used as the first current collector 1 , and an RF sputtering copper layer of ⁇ was used as the second current collector 3.
- a plurality of oxidized nanowire arrays 2 are grown on the first current collector 1, and the length of the oxidized nanowires is 20 ⁇ m.
- There is a separation gap between the piezoelectric nanowire arrays 2 each of the piezoelectric nanowire arrays 2 has a size of 3 mm ⁇ 40 mm, and a size of the separation gap is 5 mm ⁇ 40 mm; the piezoelectric nanowire array 2 is covered with the polymer insulation.
- the second collector 3 is covered on the polymer insulating layer 7.
- the active material of the negative electrode material layer 6 is graphite.
- the active material of the positive electrode material layer 4 is lithium manganate.
- a conventional single-layer polypropylene microporous membrane (PP) was used as the polymer membrane 5.
- An ethylene carbonate solution in which LiPF 6 was dissolved at a concentration of 1 mol/L was used as an electrolyte.
- the positive electrode material layer 4, the polymer separator 5 and the negative electrode material layer 6 are sequentially spaced apart in the separation gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 is connected to the first current collector 1, and the negative electrode material layer 6 and the second Collector 3 is connected.
- An electrolyte (not shown) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6.
- the specific oxidation method of the nanowires is as follows: using an equimolar amount of cyclohexamethylenetetramine (HMTA) and nitric acid hexahydrate (ZnN0 3 .6 (H 2 0)) at a concentration of 0.1 mol/L
- HMTA cyclohexamethylenetetramine
- ZnN0 3 .6 (H 2 0) nitric acid hexahydrate
- the composition of the culture solution, the formation of the aluminum foil has an oxidized seed layer Face down, placed on top of the culture medium and grown at 85 °C for 20 hours in a mechanical convection oven (Model: Yamato DKN400, Santa Clara, Calif.).
- the aluminum foil grown with the oxidized nanowires was rinsed with deionized water and dried in air.
- Graphite (average particle diameter: 20 ⁇ m) and ethanol were mixed to obtain a slurry for a negative electrode material layer having a solid content of 20% by mass.
- the anode material layer slurry is applied in the separation gap of the piezoelectric nanowire array 2 with respect to the polymer separator.
- the coating amount of the slurry to the dry mass of the material layer reaches the 15mg / cm 2.
- the mixture was dried at a temperature of 50 ° C for 15 minutes, and the solvent was removed to obtain a negative electrode material layer 6.
- An electrolyte (a solution of ethylene carbonate in which LiPF6 is dissolved at a concentration of 1 mol/L) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6 (not shown), and then the radio frequency is utilized.
- the copper layer (second current collector) 3 was placed on the polymer insulating layer 7 and the negative electrode material layer 6 by sputtering, and then encapsulated with an epoxy resin to obtain a self-charging lithium ion battery sample 2#.
Abstract
A self-charging lithium-ion battery, comprising: a first current collector (1), piezoelectric nanowire arrays (2), a second current collector (3), a positive electrode material layer (4), a polymer diaphragm (5), a negative electrode material layer (6), an electrolyte and a macromolecule insulation layer (7), wherein the first current collector (1) is arranged in parallel with the second current collector (3); a plurality of piezoelectric nanowire arrays (2) are arranged between the first current collector (1) and the second current collector (3), and the piezoelectric nanowire arrays (2) are mutually provided therebetween with a separation gap; the macromolecule insulation layer (7) covers the piezoelectric nanowire arrays (2); and the positive electrode material layer (4), the polymer diaphragm (5) and the negative electrode material layer (6) are arranged in the separation gaps of the piezoelectric nanowire arrays (2) in sequence at intervals. Under the action of a pressure or ultrasonic wave, in the case of no external power source, the self-charging lithium-ion battery of the present invention can enter a charging state and reach a fully charged state.
Description
自充电锂离子电池 技术领域 Self-charging lithium ion battery
本发明涉及一种锂离子电池， 尤其是涉及一种能够同步收获能量和储存 电荷的自充电锂离子电池。 背景技术 The present invention relates to a lithium ion battery, and more particularly to a self-charging lithium ion battery capable of simultaneously harvesting energy and storing electric charge. Background technique
锂离子电池是一种充电电池， 由于其应用方便， 便于携带等优点， 在日 常生活中被广泛应用。 锂离子电池是由锂电池发展而来的， 其由正极、 电解 质、 负极、 聚合物隔膜组成。 正极材料通常采用含锂离子的化合物， 例如锰 酸锂、 钴酸锂、 镍钴锰酸锂等。 聚合物隔膜上通常设有微孔结构， 可以让锂 离子自由通过， 而电子不能通过。 锂离子电池工作原理为： 充电时， Li+从正 极脱嵌， 经过电解质嵌入负极， 负极处于富锂状态； 放电时， Li+从负极脱嵌， 经过电解质回到正极。 传统锂离子电池依靠外部电源才能完成自身的充电， 电池只是电荷的储存装置。 Lithium-ion battery is a kind of rechargeable battery, which is widely used in daily life because of its convenient application and portability. Lithium-ion batteries are developed from lithium batteries, which consist of a positive electrode, an electrolyte, a negative electrode, and a polymer separator. The positive electrode material usually employs a compound containing lithium ions, such as lithium manganate, lithium cobaltate, lithium nickel cobalt manganese oxide, or the like. The polymer membrane is usually provided with a microporous structure, allowing lithium ions to pass freely, and electrons cannot pass. The working principle of the lithium ion battery is as follows: When charging, Li + is deintercalated from the positive electrode, and the electrolyte is inserted into the negative electrode, and the negative electrode is in a lithium-rich state; when discharging, Li + is deintercalated from the negative electrode and returns to the positive electrode through the electrolyte. Traditional lithium-ion batteries rely on an external power source to complete their own charging. The battery is just a charge storage device.
对于便携式电子产品和电动车辆，锂离子电池是它们最重要的电源之一。 对锂离子电池充电， 通常需要外部电源提供恒定的电流或电压。 因此， 在出 差、 停电等一些有可能缺少外部电源的情况下， 锂离子电池的充电会存在一 定的困难， 从而会对人们的使用引起不便。 For portable electronics and electric vehicles, lithium-ion batteries are one of their most important power sources. Charging a Li-Ion battery usually requires an external power supply to provide a constant current or voltage. Therefore, in the case of some shortcomings such as a trip, a power outage, and the like, there is a possibility that the charging of the lithium ion battery may be difficult, which may cause inconvenience to people.
压电材料是受到压力作用时会在两端面间出现电压的晶体材料， 压电材 料可以因机械形变产生电场。 以往压电材料的尺寸是几微米至几十微米， 然 而随着科技的日益发展， 该尺寸已不能满足需要。 近年随着纳米技术的发展， 越来越多的纳米压电材料被研制出来， 并应用在科研、 生活、 工业生产的各 个领域。 A piezoelectric material is a crystalline material that generates a voltage between both end faces when subjected to pressure, and the piezoelectric material can generate an electric field due to mechanical deformation. In the past, the size of piezoelectric materials was several micrometers to several tens of micrometers, but with the development of technology, this size is no longer sufficient. In recent years, with the development of nanotechnology, more and more nano-piezoelectric materials have been developed and applied in various fields of scientific research, life, and industrial production.
2006年， 美国佐治亚理工学院教授王中林等成功地在纳米尺度范围内将 机械能转换成电能， 研制出世界上最小的发电机-纳米发电机。 纳米发电机的 基本原理是： 当纳米线 （NWs )在外力下动态拉伸时， 纳米线中生成压电电
势， 相应瞬变电流在两端流动以平衡费米能级。 In 2006, Professor Wang Zhonglin of the Georgia Institute of Technology in the United States successfully converted mechanical energy into electrical energy in the nanometer scale to develop the world's smallest generator-nano generator. The basic principle of nanogenerators is: When nanowires (NWs) are dynamically stretched under external forces, piezoelectric wires are generated in the nanowires. Potential, the corresponding transient current flows at both ends to balance the Fermi level.
目前并没有技术或构思能将压电材料或纳米发电机应用到锂离子电池 中， 以使锂离子电池在不需要外加电源的情况下完成充电。 发明内容 There is currently no technology or concept to apply piezoelectric materials or nanogenerators to lithium-ion batteries so that lithium-ion batteries can be charged without the need for an external power source. Summary of the invention
本发明所要解决的技术问题是： 克服现有锂离子电池需要外部电源充电 的缺陷， 提供一种自充电锂离子电池， 能够应用纳米发电机产生的电场完成 锂离子电池的充电， 使用便捷， 特别适用于外部电源匮乏的场合。 The technical problem to be solved by the invention is: overcome the defect that the existing lithium ion battery needs external power supply charging, and provide a self-charging lithium ion battery, which can apply the electric field generated by the nano generator to complete the charging of the lithium ion battery, and is convenient to use, especially Suitable for applications where external power is scarce.
本发明的自充电锂离子电池， 由于其利用了高能量转换效率的纳米发电 机， 从而在压力或超声波作用下， 能够为锂离子从正极移动到负极并嵌入提 供足够的电势， 这样， 本发明的自充电锂离子电池会处于充电状态。 重复上 述施加压力或超声波一纳米发电机产生电势一锂离子从正极移动到负极并嵌 入的过程， 能够使本发明锂离子电池达到完全充满的状态。 本发明自充电锂 离子电池具有在各种领域中应用的潜能。 The self-charging lithium ion battery of the present invention can utilize the nano-generator with high energy conversion efficiency to provide sufficient potential for lithium ions to move from the positive electrode to the negative electrode and embed under pressure or ultrasonic waves. Thus, the present invention The self-charging lithium-ion battery will be charged. Repeating the above-described application of pressure or ultrasonic-nano generator to generate a potential - a process in which lithium ions are moved from the positive electrode to the negative electrode and embedded, enables the lithium ion battery of the present invention to reach a fully charged state. The self-charging lithium ion battery of the present invention has potential for application in various fields.
为了解决上述技术问题， 本发明提供的第一技术方案是， 一种自充电锂 离子电池， 包括第一集电器 1 , 压电纳米线阵列 2, 第二集电器 3 , 正极材料层 4, 聚合物隔膜 5 , 负极材料层 6, 电解质（图未示）， 以及高分子绝缘层 7; 第 一集电器 1与第二集电器 3平行放置； 多个压电纳米线阵列 2横跨第一集电器 1 和第二集电器 3设置在第一集电器 1与第二集电器 3之间， 且压电纳米线阵列 2 相互之间存在分隔间隙；所述压电纳米线阵列 2上覆盖有所述高分子绝缘层 7; 正极材料层 4 , 聚合物隔膜 5和负极材料层 6依次间隔设置在压电纳米线阵列 2 的分隔间隙中，且正极材料层 4或负极材料层 6分别与第一集电器 1或第二集电 器 3连接； 以及分别在正极材料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料 层 6之间填充电解质 （图未示）。 In order to solve the above technical problem, the first technical solution provided by the present invention is a self-charging lithium ion battery, comprising a first current collector 1, a piezoelectric nanowire array 2, a second current collector 3, a positive electrode material layer 4, and a polymerization. a separator 5, a negative electrode material layer 6, an electrolyte (not shown), and a polymer insulating layer 7; the first current collector 1 and the second current collector 3 are placed in parallel; the plurality of piezoelectric nanowire arrays 2 span the first set The electric appliance 1 and the second current collector 3 are disposed between the first current collector 1 and the second current collector 3, and the piezoelectric nanowire array 2 has a separation gap therebetween; the piezoelectric nanowire array 2 is covered with a gap The polymer insulating layer 7; the positive electrode material layer 4, the polymer separator 5 and the negative electrode material layer 6 are sequentially disposed in the separation gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 or the negative electrode material layer 6 respectively and the first The current collector 1 or the second current collector 3 is connected; and an electrolyte (not shown) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6, respectively.
所有压电纳米线层作为一个整体被分隔成多个分块区， 每个分块区即为 一个压电纳米线阵列 2, 因此形成多个彼此之间存在分隔间隙的压电纳米线阵 列 2。 本发明对压电纳米线阵列 2的分隔方式没有特殊规定， 满足压电纳米线 阵列 2相互之间存在分隔间隙， 且分隔间隙能够放置正极材料层 4、 聚合物隔
膜 5和负极材料层 6的分隔方式， 如井字分割、 米字分割、 斑马线分割等， 都 在本发明的保护范围之内。 All of the piezoelectric nanowire layers are divided into a plurality of blocking regions as a whole, and each of the blocking regions is a piezoelectric nanowire array 2, thereby forming a plurality of piezoelectric nanowire arrays 2 having a separation gap therebetween . The present invention does not specifically define the separation mode of the piezoelectric nanowire array 2, and satisfies the existence of a separation gap between the piezoelectric nanowire arrays 2, and the separation gap can place the positive electrode material layer 4 and the polymer spacer. The separation of the film 5 and the negative electrode material layer 6, such as well-segmentation, m-square segmentation, zebra-line segmentation, etc., is within the scope of the present invention.
前述的自充电锂离子电池， 所述第一集电器和第二集电器所用材料分别 独立的选自铝、 铜、 镍、 聚苯胺、 聚乙炔、 聚吡咯、 聚噻吩、 聚对位亚苯基 或聚苯乙炔。 In the foregoing self-charging lithium ion battery, the materials used in the first current collector and the second current collector are independently selected from the group consisting of aluminum, copper, nickel, polyaniline, polyacetylene, polypyrrole, polythiophene, polyparaphenylene Or polyphenylacetylene.
前述的自充电锂离子电池， 所述压电材料是氧化辞纳米线、 锆钛酸铝纳 米线或钛酸钡纳米线。 In the above self-charging lithium ion battery, the piezoelectric material is an oxidized nanowire, a zirconium titanate nanowire or a barium titanate nanowire.
前述的自充电锂离子电池，所述高分子绝缘层 7所用材料是聚曱基丙烯酸 曱酯或聚二曱基硅氧烷。 In the above self-charging lithium ion battery, the material of the polymer insulating layer 7 is polydecyl acrylate or polydithiosiloxane.
前述的自充电锂离子电池， 所述负极材料层中所用活性材料是石墨， 碳 纳米管， 碳纤维。 In the above self-charging lithium ion battery, the active material used in the negative electrode material layer is graphite, carbon nanotubes, and carbon fibers.
前述的自充电锂离子电池， 所述正极材料层中所用活性材料是锰酸锂、 磷酸铁锂、 钴酸锂或 Li-Ni-Co-Mn-0三元正极材料。 In the above self-charging lithium ion battery, the active material used in the positive electrode material layer is lithium manganate, lithium iron phosphate, lithium cobaltate or Li-Ni-Co-Mn-0 ternary positive electrode material.
前述的自充电锂离子电池， 以井字分割、 米字分割或斑马线分割的分隔 方式， 形成多个相互之间存在分隔间隙的压电纳米线阵列 2。 In the above self-charging lithium ion battery, a plurality of piezoelectric nanowire arrays 2 having a separation gap therebetween are formed by a well division, a rice division or a zebra crossing.
以压电纳米材料阵列为基础的纳米发电机具有高能量转换效率， 在压力 或超声波作用下， 能够将锂离子从正极移动到负极并嵌入。 本发明自充电锂 离子电池在压力或超声波作用下， 不需要外部电源就能够进行充电并达到完 全充满的状态。 本发明自充电锂离子电池能够应用于手机、 无线信号接收发 射等电子产品， 特别适用于外部电源匮乏的场合。 附图说明 Nanogenerators based on piezoelectric nanomaterial arrays have high energy conversion efficiencies and can move lithium ions from the positive electrode to the negative electrode and embed under pressure or ultrasonic waves. The self-charging lithium ion battery of the present invention can be charged and fully charged without the need of an external power source under pressure or ultrasonic waves. The self-charging lithium ion battery of the invention can be applied to electronic products such as mobile phones, wireless signal receiving and transmitting, and is particularly suitable for occasions where external power is scarce. DRAWINGS
图 1是本发明自充电锂离子电池结构图。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a structural view of a self-charging lithium ion battery of the present invention.
图 2是本发明自充电锂离子电池的工作原理图。 具体实施方式 2 is a schematic view showing the operation of the self-charging lithium ion battery of the present invention. detailed description
为充分了解本发明之目的、 特征及功效， 借由下述具体的实施方式， 对 本发明做详细说明。
本发明的自充电锂离子电池， 采用以压电纳米材料阵列为基础的纳米发 电机进行发电。 由于该纳米发电机具有高能量转换效率， 从而在压力或超声 波作用下， 能够为锂离子从正极移动到负极并嵌入提供足够的电势。 The present invention will be described in detail by the following detailed description of the invention. The self-charging lithium ion battery of the present invention uses a nano-generator based on a piezoelectric nano material array for power generation. Since the nanogenerator has high energy conversion efficiency, under the action of pressure or ultrasonic waves, it can provide sufficient potential for lithium ions to move from the positive electrode to the negative electrode and embed.
如图 1 所示， 一种自充电锂离子电池， 包括第一集电器 1 , 压电纳米线 阵列 2, 第二集电器 3 , 正极材料层 4, 聚合物隔膜 5 , 负极材料层 6, 电解 质（图未示）， 以及高分子绝缘层 7; 第一集电器 1与第二集电器 3平行放置； 多个压电纳米线阵列 2横跨第一集电器 1和第二集电器 3间隔设置在第一集 电器 1与第二集电器 3之间， 且压电纳米线阵列 2相互之间存在分隔间隙； 所述压电纳米线阵列 2上覆盖有所述高分子绝缘层 7; 正极材料层 4, 聚合物 隔膜 5和负极材料层 6依次间隔设置在压电纳米线阵列 2的分隔间隙中， 且 正极材料层 4或负极材料层 6分别与第一集电器 1或第二集电器 3连接； 以 及分别在正极材料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料层 6之间 填充电解质 （图未示）。 As shown in FIG. 1 , a self-charging lithium ion battery includes a first current collector 1 , a piezoelectric nanowire array 2 , a second current collector 3 , a positive electrode material layer 4 , a polymer separator 5 , a negative electrode material layer 6 , and an electrolyte (not shown), and the polymer insulating layer 7; the first current collector 1 and the second current collector 3 are placed in parallel; the plurality of piezoelectric nanowire arrays 2 are spaced apart across the first current collector 1 and the second current collector 3 Between the first current collector 1 and the second current collector 3, and the piezoelectric nanowire array 2 has a separation gap therebetween; the piezoelectric nanowire array 2 is covered with the polymer insulation layer 7; The layer 4, the polymer separator 5 and the anode material layer 6 are sequentially disposed in the separation gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 or the negative electrode material layer 6 and the first current collector 1 or the second current collector 3, respectively. And connecting an electrolyte (not shown) between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6, respectively.
在一个具体的实施方式中， 压电纳米线生长在第一集电器 1上， 压电纳 米线作为整体被分割成多个分块区， 每个分块区即为一个压电纳米线阵列 2, 因此形成多个相互之间存在分隔间隙的压电纳米线阵列 2;压电纳米线阵列 2 上覆盖有所述高分子绝缘层 7。 正极材料层 4, 聚合物隔膜 5和负极材料层 6 依次间隔设置在压电纳米线阵列 2的间隙中， 且正极材料层 4与第一集电器 1的表面连接。 在高分子绝缘层 7和负极材料层 6上设有第二集电器 3 , 且负 极材料层 6与第二集电器 3连接。 In a specific embodiment, the piezoelectric nanowires are grown on the first current collector 1, and the piezoelectric nanowires are divided into a plurality of blocking regions as a whole, and each of the blocking regions is a piezoelectric nanowire array 2 Therefore, a plurality of piezoelectric nanowire arrays 2 having a separation gap therebetween are formed; the piezoelectric nanowire array 2 is covered with the polymer insulating layer 7. The positive electrode material layer 4, the polymer separator 5 and the negative electrode material layer 6 are sequentially disposed in the gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 is connected to the surface of the first current collector 1. A second current collector 3 is provided on the polymer insulating layer 7 and the negative electrode material layer 6, and the negative electrode material layer 6 is connected to the second current collector 3.
优选的， 第一集电器 1和第二集电器 3所用材料只要是有导电性的物质 即可， 例如可以为铝、 铜、 镍、 聚苯胺、 聚乙炔、 聚吡咯、 聚噻吩、 聚对位 亚苯基、 聚苯乙炔等。 进而， 本发明对第一集电器 1和第二集电器 3的形状 没有特别限定， 厚度通常在 5 ~ ΙΟΟ μ ηι, 优选 10 ~ 15 μ ηι。 Preferably, the materials used in the first current collector 1 and the second current collector 3 are as long as they are electrically conductive, and may be, for example, aluminum, copper, nickel, polyaniline, polyacetylene, polypyrrole, polythiophene, poly-alignment. Phenylene, polyphenylacetylene, etc. Further, the shape of the first current collector 1 and the second current collector 3 is not particularly limited, and the thickness is usually 5 to ΙΟΟ μ ηι, preferably 10 to 15 μ η.
优选的， 压电材料是氧化辞纳米线、 锆钛酸铝纳米线或钛酸钡纳米线。 所述纳米线的尺寸大约是直径 100-200nm、 长度 20 μ ηι左右。 Preferably, the piezoelectric material is an oxidized nanowire, an aluminum zirconate titanate nanowire or a barium titanate nanowire. The nanowires have a size of about 100-200 nm in diameter and about 20 μηη in length.
优选的所述高分子绝缘层 7所用材料是聚曱基丙烯酸曱酯或聚二曱基硅 氧烷。
在超声波或压力作用下， 压电纳米线阵列 2产生感应电动势。 由于采用 了高分子绝缘层， 绝缘层的存在提供了一个无限高的势垒， 因此在第一集电 器 1和第二集电器 3之间形成感应电场。 高分子绝缘层在压电纳米线上形成 覆盖层， 同时覆盖层也包覆在压电纳米线阵列顶端和周围， 在压电纳米线承 受电场作用时， 提高了电池结构的稳定性。 The material of the polymer insulating layer 7 is preferably polydecyl methacrylate or polydithiosiloxane. The piezoelectric nanowire array 2 generates an induced electromotive force under the action of ultrasonic waves or pressure. Due to the use of the polymer insulating layer, the presence of the insulating layer provides an infinitely high barrier, thus forming an induced electric field between the first current collector 1 and the second current collector 3. The polymer insulating layer forms a coating layer on the piezoelectric nanowire, and the covering layer is also coated on the top and the periphery of the piezoelectric nanowire array. When the piezoelectric nanowire is subjected to an electric field, the stability of the battery structure is improved.
在锂离子电池中， 充电过程中负极接受锂离子， 正极释放锂离子； 而放 电过程中负极释放锂离子， 正极接受锂离子。 锂离子电池的正极和负极通常 包括集电器和设置在集电器上的材料层。 In a lithium ion battery, the negative electrode receives lithium ions during charging, and the positive electrode releases lithium ions; while in the discharge process, the negative electrode releases lithium ions, and the positive electrode receives lithium ions. The positive and negative electrodes of a lithium ion battery typically include a current collector and a layer of material disposed on the current collector.
材料层中含有电极活性材料。本发明对负极所用活性材料没有特殊要求， 常规锂离子电池负极用活性材料均可以应用于本发明， 常规的应用于锂离子 电池的负极活性物质包括碳材料及其复合物， 例如石墨、 非晶态碳、 碳纤维、 焦碳、 活性碳等碳材料， 以及碳材料和硅、 锡、 银等金属或这些金属的氧化 物形成的复合物。 本发明对正极所用活性材料没有特殊要求， 常规锂离子电 池正极用活性材料均可以应用于本发明， 例如锰酸锂、 騎酸铁锂、 钴酸锂、 Li-Ni-Co-Mn-0三元正极材料等。 The material layer contains an electrode active material. The present invention has no special requirements for the active material used for the negative electrode, and the active material for the negative electrode of the conventional lithium ion battery can be applied to the present invention. The negative active material used in the conventional lithium ion battery includes the carbon material and its composite, such as graphite and amorphous. A carbon material such as carbon, carbon fiber, coke or activated carbon, and a composite of a carbon material and a metal such as silicon, tin or silver or an oxide of these metals. The invention has no special requirement for the active material used for the positive electrode, and the active material for the positive electrode of the conventional lithium ion battery can be applied to the invention, for example, lithium manganate, lithium iron oxide, lithium cobalt oxide, Li-Ni-Co-Mn-0 Elementary cathode material, etc.
本发明对聚合物隔膜所用材料没有特殊要求， 常规锂离子电池用聚合物 隔膜均可以应用于本发明， 例如单层聚丙烯微孔膜（PP ), 单层聚乙烯微孔膜 ( PE ), 多层聚丙烯微孔膜， 多层聚乙烯微孔膜等。 The present invention has no special requirements for the materials used for the polymer separator. Conventional polymer separators for lithium ion batteries can be applied to the present invention, such as a single-layer polypropylene microporous membrane (PP), a single-layer polyethylene microporous membrane (PE), Multilayer polypropylene microporous membrane, multilayer polyethylene microporous membrane, etc.
本发明对电解质没有特殊要求， 常规锂离子电池用电解质均可以应用于 本发明。 常规电解质由有机溶剂和电解质锂盐组成。 常用的电解质锂盐有 LiC104、 LiBF4、 Lil、 LiPF6、 LiCF3S03、 LiCF3C02、 LiAsF6、 LiSbF6、 LiAlCl4、 LiCl、 LiBr、 LiB(C2H5)4、 LiCH3S03、 LiC4F9S03、 Li(CF3S02)2N、 Li[(C02)2]2B 等。 常规有机溶剂有酯类和醚类有机溶剂， 例如碳酸乙烯酯、 碳酸丙烯酯、 碳酸二曱酯、 碳酸二乙酯等碳酸酯类， γ -丁内酯等内酯类， 二曱氧曱烷、 三 曱氧基曱烷、 1,2-二曱氧基乙烷、 四氢呋喃、 2-曱基四氢呋喃等醚类， 二曱基 亚砜等亚砜类， 1,3-二氧戊环、 4-曱基 -1,3-二氧戊环等氧戊环类， 乙腈、 硝基 曱烷等含氮类， 曱酸曱酯、 乙酸曱酯、 乙酸丁酯、 丙酸曱酯等酯类， 二甘醇 二曱醚、 三甘醇二曱醚、 四甘醇二曱醚等甘醇二曱醚类， 丙酮、 二乙基酮、
曱基乙基酮、 曱基异丁基酮等酮类， 环丁砜等砜类， 1,3-丙烷石黄内酯、 4-丁烷 磺内酯等磺内酯类。 The present invention has no particular requirements for electrolytes, and conventional electrolytes for lithium ion batteries can be applied to the present invention. A conventional electrolyte consists of an organic solvent and an electrolyte lithium salt. Commonly used electrolyte lithium salts are LiC10 4 , LiBF 4 , Lil , LiPF 6 , LiCF 3 S0 3 , LiCF 3 C0 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiCl, LiBr, LiB(C 2 H 5 ) 4 , LiCH 3 S0 3 , LiC 4 F 9 S0 3 , Li(CF 3 S0 2 ) 2 N, Li[(C0 2 ) 2 ] 2 B, and the like. Conventional organic solvents include ester and ether organic solvents, such as ethylene carbonate, propylene carbonate, dinonyl carbonate, diethyl carbonate, and the like, γ-butyrolactone and the like, dioxane. , ethers such as trimethoxy decane, 1,2-dimethoxy ethane, tetrahydrofuran, 2-mercaptotetrahydrofuran, sulfoxides such as dimethyl sulfoxide, 1,3-dioxolane, 4 - anthracene-1,3-dioxolane and other oxylanes, acetonitrile, nitrodecane and other nitrogen-containing compounds, decyl decanoate, decyl acetate, butyl acetate, decyl propionate and the like, Glycol diterpene ether such as diethylene glycol dioxime ether, triethylene glycol dioxime ether or tetraethylene glycol diterpene ether, acetone, diethyl ketone, a ketone such as mercaptoethyl ketone or decyl isobutyl ketone; a sulfone such as sulfolane; a sultone such as 1,3-propane yellow lactone or 4-butane sultone.
优选的， 该自充电锂离子电池用环氧基树脂封装。 Preferably, the self-charging lithium ion battery is encapsulated with an epoxy resin.
本发明对第一集电器 1 , 压电纳米线阵列 2, 第二集电器 3 , 正极 4, 聚 合物隔膜 5, 负极 6以及高分子绝缘层 7的尺寸没有特殊要求， 本领域技术 人员可以根据自充电锂离子电池应用领域的不同，也可以根据需要的电容量， 调整上述元件的尺寸和规格。 本发明构思的独特之处在于将纳米发电机应用 到锂离子电池中， 在压力或超声波作用下， 高能量转换效率的纳米发电机能 够为锂离子从正极移动到负极并嵌入提供足够的电势。 The present invention has no special requirements on the sizes of the first current collector 1, the piezoelectric nanowire array 2, the second current collector 3, the positive electrode 4, the polymer separator 5, the negative electrode 6, and the polymer insulating layer 7, and those skilled in the art can Different from the field of application of self-charging lithium-ion batteries, it is also possible to adjust the size and specifications of the above components according to the required capacitance. The inventive concept is unique in that a nanogenerator is applied to a lithium ion battery, and a high energy conversion efficiency nanogenerator can provide sufficient potential for lithium ions to move from the positive electrode to the negative electrode and be embedded under pressure or ultrasonic waves.
下面详细说明本发明自充电锂离子电池的工作原理。 如图 2所示， 在外 加压力或超声波作用下， 由于压电效应， 压电材料纳米阵列两端分别产生正 电荷和负电荷， 第一集电器和第二集电器分别与正极材料层或负极材料层连 接， 该电场为锂离子从正极转移到负极并嵌入提供足够的电势。 这样， 本发 明自充电锂离子电池的电化学***处于充电状态，即锂离子从正电极材料（以 LiCo02为例： LiCo02→ Li1-xCo02 + xLi+ + xe" )移动至负电极材料（以石墨 为例： Li+ + e- + 6C LiC6 )。 重复多次施加压力或超声波， 电池能够充满。 The working principle of the self-charging lithium ion battery of the present invention will be described in detail below. As shown in FIG. 2, under the action of external pressure or ultrasonic wave, due to the piezoelectric effect, positive and negative charges are respectively generated at the two ends of the piezoelectric material nano-array, and the first current collector and the second current collector respectively form a positive electrode material layer or a negative electrode. The material layer is connected, and the electric field provides sufficient potential for lithium ions to be transferred from the positive electrode to the negative electrode and embedded. Thus, since the rechargeable lithium ion battery according to the present invention is an electrochemical system in a charging state, i.e., lithium ions from the positive electrode material (in LiCo0 2 Example: LiCo0 2 → Li 1-x Co0 2 + xLi + + xe ") moves to the negative electrode Material (taking graphite as an example: Li + + e- + 6C LiC 6 ). Repeatedly applying pressure or ultrasonic waves, the battery can be filled.
下面详细说明本发明自充电锂离子电池的制备方法， 但需要注意的是， 这并不作为对本发明的限制， 而仅仅是示例性说明。 The preparation method of the self-charging lithium ion battery of the present invention will be described in detail below, but it should be noted that this is not intended to limit the invention, but is merely illustrative.
S1.压电纳米线阵列 2的生长 S1. Growth of Piezoelectric Nanowire Array 2
用常规喷射溅镀在第一集电器 1的一个面上生成氧化辞种子层。 在氧化 辞种子层上光刻常规光阻材料， 用微加工平板印刷法在光阻材料上开一个个 规则的方形窗阵列， 方形窗口内区域生长压电纳米线阵列 2, 方形窗口间隙 存在光阻材料而使氧化辞纳米线无法生长。 An oxidized seed layer is formed on one face of the first current collector 1 by conventional spray sputtering. A conventional photoresist material is photolithographically patterned on the oxidized seed layer, and a regular square window array is opened on the photoresist material by microfabrication lithography, and the piezoelectric nanowire array 2 is grown in the square window region, and the square window gap exists in the light. Resisting the material makes the oxidized nanowires unable to grow.
具体的氧化辞纳米线的生长方法如下： 采用 0.1mol/L浓度的由等摩尔的 环六亚曱基四胺（ HMTA )和硝酸辞六水合物 （ ZnN03.6(H20) )组成的培养 液， 将第一集电器 1 的生成有氧化辞种子层的面朝下， 放在培养液顶部， 在 85 °C下在机械对流加热炉（型号： Yamato DKN400 ,加利福尼亚， 圣克拉拉 ) 中生长 16小时。用去离子水沖洗生长有氧化辞纳米线的第一集电器 1并在空
气中干燥。 剥落所有剩余光阻材料， 并对纳米线阵列加热退火（优选 145-155 °C ), 得到多个相互之间存在分隔间隙的压电纳米线阵列 2。 然后通过旋涂将 高分子绝缘层 7 (优选聚曱基丙烯酸曱酯层）涂覆于压电纳米线阵列 2上。 The specific oxidation method of the nanowires is as follows: 0.1 mol/L concentration consisting of equimolar cyclohexamethylenetetramine (HMTA) and nitric acid hexahydrate (ZnN0 3 .6(H 2 0) ) The culture solution, the first current collector 1 is formed with the oxidized seed layer facing down, placed on top of the culture solution, at 85 ° C in a mechanical convection oven (Model: Yamato DKN400, Santa Clara, California) Growing in 16 hours. Flushing the first current collector 1 with the oxidized nanowires with deionized water and empty Dry in the air. All of the remaining photoresist material is peeled off, and the nanowire array is thermally annealed (preferably 145-155 ° C) to obtain a plurality of piezoelectric nanowire arrays 2 having a separation gap therebetween. Then, a polymer insulating layer 7 (preferably a polydecyl methacrylate layer) is applied onto the piezoelectric nanowire array 2 by spin coating.
本发明对所用光阻材料没有特殊要求， 常规用于基板光刻蚀的光阻材料 均可应用于本发明， 例如包括 5-60质量百分比感光树脂（例如环氧树脂改性 物），5-50质量百分比的反应性稀释剂（例如聚乙二醇二曱基丙烯酸酯）, 0.1-15 质量百分比的光引发剂。 The present invention has no special requirements for the photoresist material used, and a photoresist material conventionally used for substrate photolithography can be applied to the present invention, for example, including 5-60 mass% photosensitive resin (for example, epoxy resin modified), 5- 50 mass percent reactive diluent (e.g., polyethylene glycol dimercapto acrylate), 0.1-15 mass percent photoinitiator.
S2. 正极材料层 4的生成 S2. Generation of positive electrode material layer 4
521. 将正极活性材料和溶剂混合， 得到正极材料层用浆料。 电极活性材 料如上所述， 这里不再赘述。 本发明对材料层用溶剂没有特殊要求， 常规锂 离子电池材料层用溶剂均可应用于本发明， 例如水， 以及在含有曱醇、 乙醇、 正丙醇、 异丙醇或正丁醇等低级醇的水溶液。 本发明正极材料层用浆料中固 体成分为 10-60质量％。 521. The positive electrode active material and the solvent are mixed to obtain a slurry for the positive electrode material layer. The electrode active material is as described above and will not be described herein. The present invention has no special requirements for the solvent for the material layer, and a solvent for the conventional lithium ion battery material layer can be applied to the present invention, such as water, and at a low level containing decyl alcohol, ethanol, n-propanol, isopropanol or n-butanol. An aqueous solution of an alcohol. The solid content of the slurry for a positive electrode material layer of the present invention is from 10 to 60% by mass.
在制备正极材料层用浆料时， 优选混入聚合物粘结材料和传导石墨， 例 如活性物质： 乙炔黑： 聚四氟乙烯的质量比为 85: 10: 5。 In the preparation of the slurry for the positive electrode material layer, it is preferred to incorporate a polymer binder and conductive graphite, for example, an active material: acetylene black: polytetrafluoroethylene has a mass ratio of 85:10:5.
522. 在第一集电器 1面上， 在压电纳米线阵列 2的分隔间隙中涂布正极 材料层浆料。 涂布可以使用常规方法， 例如转印辊、 涂布机等进行。 浆料的 涂布量为了使材料层的干燥质量达到 10 ~ 15mg/cm2。 522. On the first current collector 1 side, a positive electrode material layer slurry is applied in the separation gap of the piezoelectric nanowire array 2. The coating can be carried out using a conventional method such as a transfer roller, a coater or the like. The coating amount of the slurry is such that the dry mass of the material layer reaches 10 to 15 mg/cm 2 .
523. 在 50 ~ 70 °C的温度下干燥处理 3-15分钟， 将溶剂除去。 523. Dry at a temperature of 50 to 70 °C for 3-15 minutes to remove the solvent.
S3. 放置聚合物隔膜 5 S3. Place the polymer separator 5
在压电纳米线阵列 1的分隔间隙中， 相对正极材料层 4间隔的放置聚合 物隔膜 5。 In the separation gap of the piezoelectric nanowire array 1, the polymer separator 5 is placed spaced apart from the positive electrode material layer 4.
S4.负极材料层 6的生成 S4. Generation of negative electrode material layer 6
S41. 将负极活性材料和溶剂混合， 得到负极材料层用浆料。 电极活性材 料如上所述， 这里不再赘述。 本发明对材料层用溶剂没有特殊要求， 常规锂 离子电池材料层用溶剂均可应用于本发明， 例如水， 以及在含有曱醇、 乙醇、 正丙醇、 异丙醇或正丁醇等低级醇的水溶液。 本发明负极材料层用浆料中固 体成分为 10-60质量％。
542. 相对聚合物隔膜间隔的， 在压电纳米线阵列 2的分隔间隙中涂布负 极材料层浆料。 浆料的涂布量为了使材料层的干燥质量达到 10 ~ 15mg/cm2。 S41. The negative electrode active material and the solvent are mixed to obtain a slurry for the negative electrode material layer. The electrode active material is as described above and will not be described herein. The present invention has no special requirements for the solvent for the material layer, and a solvent for the conventional lithium ion battery material layer can be applied to the present invention, such as water, and at a low level containing decyl alcohol, ethanol, n-propanol, isopropanol or n-butanol. An aqueous solution of an alcohol. The solid content of the slurry for a negative electrode material layer of the present invention is from 10 to 60% by mass. 542. The anode material layer slurry is coated in the separation gap of the piezoelectric nanowire array 2 with respect to the polymer separator. The coating amount of the slurry is such that the dry mass of the material layer reaches 10 to 15 mg/cm 2 .
543. 在 50 ~ 70 °C的温度下干燥处理 3-15分钟， 将溶剂除去。 543. Dry at a temperature of 50 to 70 °C for 3-15 minutes to remove the solvent.
S5. 在正极材料层 4与聚合物隔膜 5、聚合物隔膜 5与负极材料层 6之间 填充电解质， 然后利用射频溅镀将第二集电器 3设置到高分子绝缘层 7和负 极材料层 6上， 然后用环氧基树脂封装， 得到自充电锂离子电池。 S5. filling an electrolyte between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6, and then disposing the second current collector 3 to the polymer insulating layer 7 and the negative electrode material layer 6 by radio frequency sputtering. Then, it is encapsulated with an epoxy resin to obtain a self-charging lithium ion battery.
当理解的是， 这不应被理解为对本发明权利要求范围的限制。 实施例 It is understood that this should not be construed as limiting the scope of the claims. Example
实施例 1 Example 1
本实施例自充电锂离子电池的整体尺寸为 40x60mm。 采用纯度 99.5%厚 度 ΙΟμηι的铝箔作为第一集电器 1 , 采用 ΙΟμηι的射频溅镀铜层作为第二集电 器 3。 多个氧化辞纳米线阵列 2生长在第一集电器 1上， 氧化辞纳米线的长 度为 20μηι。压电纳米线阵列 2之间存在分隔间隙，每个压电纳米线阵列 2的 尺寸为 3mmx40 mm, 分隔间隙的尺寸为宽度为 5 mmx40mm; 所述压电纳米 线阵列 2上覆盖有所述高分子绝缘层（聚曱基丙烯酸曱酯层） 7。 第二集电器 3覆盖在高分子绝缘层 7上。 The overall size of the self-charging lithium ion battery of this embodiment is 40 x 60 mm. An aluminum foil having a purity of 99.5% thick ΙΟμηι was used as the first current collector 1 , and an RF sputtering copper layer of ΙΟμηι was used as the second current collector 3. A plurality of oxidized nanowire arrays 2 are grown on the first current collector 1, and the length of the oxidized nanowires is 20 μm. There is a separation gap between the piezoelectric nanowire arrays 2, each of the piezoelectric nanowire arrays 2 has a size of 3 mm×40 mm, and a size of the separation gap is 5 mm×40 mm; the piezoelectric nanowire array 2 is covered with the height Molecular insulating layer (poly(decyl acrylate) layer) 7. The second current collector 3 is covered on the polymer insulating layer 7.
负极材料层 6的活性材料为石墨。 正极材料层 4的活性材料为钴酸锂。 采用常规单层聚丙烯微孔膜（PP )作为聚合物隔膜 5。 采用以 lmol/L的浓度 溶解了 LiPF6的碳酸亚乙酯溶液作为电解质。 正极材料层 4, 聚合物隔膜 5和 负极材料层 6依次间隔的设置在压电纳米线阵列 2的分隔间隙中， 且正极材 料层 4和第一集电器 1连接， 负极材料层 6与第二集电器 3连接。 在正极材 料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料层 6之间填充电解质 （图 未示）。 The active material of the negative electrode material layer 6 is graphite. The active material of the positive electrode material layer 4 is lithium cobaltate. A conventional single-layer polypropylene microporous membrane (PP) was used as the polymer membrane 5. An ethylene carbonate solution in which LiPF 6 was dissolved at a concentration of 1 mol/L was used as an electrolyte. The positive electrode material layer 4, the polymer separator 5 and the negative electrode material layer 6 are sequentially spaced apart in the separation gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 is connected to the first current collector 1, and the negative electrode material layer 6 and the second Collector 3 is connected. An electrolyte (not shown) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6.
下面说明本实施例自充电锂离子电池的制备方法。 The preparation method of the self-charging lithium ion battery of this embodiment will be described below.
用常规喷射溅镀在用作第一集电器 1的铝箔的一个面上生成厚度 lOOnm
的氧化辞种子层。 在氧化辞种子层上覆盖常规光阻材料， 用微加工平板印刷 法在光阻材料上开一个个规则的方形窗阵列， 方形窗口内区域， 棵露有氧化 辞种子， 方形窗口内区域生长压电纳米线阵列 2, 方形窗口间隙存在光阻材 料而使氧化辞纳米线无法生长。 光阻材料在随后的氧化辞纳米线生长过程中 相当于一个分区模具，使氧化辞纳米线只生长在有暴露氧化辞种子的区域内， 从而实现氧化辞纳米线阵列 2间存在空隙。 具体的氧化辞纳米线的生长方法 如下： 采用 0.1mol/L浓度的由等摩尔的环六亚曱基四胺（HMTA )和硝酸辞 六水合物（ZnN03.6(H20) )组成的培养液， 将铝箔的生成有氧化辞种子层的 面朝下， 放在培养液顶部， 在 85 °C下在机械对流加热炉 （型号： Yamato DKN400, 加利福尼亚， 圣克拉拉） 中生长 20小时。 用去离子水沖洗生长有 氧化辞纳米线的铝箔并在空气中干燥。 然后剥落所有剩余光阻材料， 并对纳 米线阵列在 150°C加热退火。 然后通过旋涂将高分子绝缘层（聚曱基丙烯酸 曱酯层）涂覆于氧化辞纳米线阵列 2上。 A thickness of 100 nm is generated on one side of the aluminum foil used as the first current collector 1 by conventional spray sputtering Oxidation of the seed layer. The conventional photoresist material is covered on the oxidized seed layer, and a regular square window array is opened on the photoresist material by micro-processing lithography. The inner area of the square window is exposed with oxidized seeds, and the growth pressure in the square window is increased. In the electrical nanowire array 2, a photoresist material exists in the square window gap to make the oxidized nanowires unable to grow. The photoresist material is equivalent to a zoned mold during the subsequent oxidation of the nanowires, so that the oxidized nanowires are only grown in the region where the exposed oxidized seeds are present, thereby realizing the presence of voids between the oxidized nanowire arrays 2. The specific oxidation method of the nanowires is as follows: 0.1 mol/L concentration consisting of equimolar cyclohexamethylenetetramine (HMTA) and nitric acid hexahydrate (ZnN0 3 .6 (H 2 0) ) The culture solution was prepared by placing the aluminum foil with the oxidized seed layer face down on the top of the culture solution and growing at 85 ° C for 20 hours in a mechanical convection oven (Model: Yamato DKN400, Santa Clara, Calif.) . The aluminum foil grown with the oxidized nanowires was rinsed with deionized water and dried in air. All remaining photoresist material was then peeled off and the nanowire array was annealed at 150 °C. Then, a polymer insulating layer (polydecyl acrylate layer) was applied onto the oxidized nanowire array 2 by spin coating.
将钴酸锂（平均粒径 10 μ ηι )、 乙炔黑、 聚四氟乙烯材料按照质量比为 85: 10: 5混合， 然后将上述混合物与 ΝΜΡ (曱基吡咯烷酮） 混合， 得到固 体成分为 20%的正极材料层用浆料。 按照材料层的干燥质量为 15mg/cm2, 将 浆料均匀地涂布在第一集电器 1面上的压电纳米线阵列 2的分隔间隙中。 接 着， 在 50°C下干燥 5分钟， 形成正极材料层 4。 在压电纳米线阵列 2的分隔 间隙中， 相对正极材料层 4间隔的放置聚合物隔膜 5。 Lithium cobaltate (average particle diameter 10 μ ηι ), acetylene black, and polytetrafluoroethylene material were mixed at a mass ratio of 85:10:5, and then the above mixture was mixed with hydrazine (mercaptopyrrolidone) to obtain a solid content of 20 % of the slurry for the positive electrode material layer. The slurry was uniformly coated in the separation gap of the piezoelectric nanowire array 2 on the surface of the first current collector 1 in accordance with the dry mass of the material layer of 15 mg/cm 2 . Next, it was dried at 50 ° C for 5 minutes to form a positive electrode material layer 4 . In the separation gap of the piezoelectric nanowire array 2, the polymer separator 5 is placed spaced apart from the positive electrode material layer 4.
将石墨（平均粒径 20 μ m )和乙醇混合， 得到固体成分为 20质量％的负 极材料层用浆料。 相对聚合物隔膜间隔的， 在压电纳米线阵列 2的分隔间隙 中涂布负极材料层浆料。 浆料的涂布量为了使材料层的干燥质量达到 15mg/cm2。 在 50°C的温度下干燥处理 15分钟， 将溶剂除去， 得到负极材料 层 6。 Graphite (average particle diameter: 20 μm) and ethanol were mixed to obtain a slurry for a negative electrode material layer having a solid content of 20% by mass. The anode material layer slurry is applied in the separation gap of the piezoelectric nanowire array 2 with respect to the polymer separator. The coating amount of the slurry was such that the dry mass of the material layer reached 15 mg/cm 2 . The mixture was dried at a temperature of 50 ° C for 15 minutes, and the solvent was removed to obtain a negative electrode material layer 6.
在正极材料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料层 6之间填 充电解质 （以 lmol/L的浓度溶解了 LiPF6的碳酸亚乙酯溶液）（图未示 ), 然 后利用射频溅镀将铜层（第二集电器） 3设置到高分子绝缘层 7和负极材料 层 6上， 然后用环氧基树脂封装， 得到自充电锂离子电池样品 1#。
将样品 1#放在 1Hz的超声波中持续 2分钟， 取出后， 进行放电测试， 以 0.02mA进行恒定电流放电， 样品 1#的放电容量为 2.3mAh。 实施例 2 An electrolyte (a solution of ethylene carbonate in which LiPF 6 is dissolved at a concentration of 1 mol/L) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6 (not shown), and then utilized. RF sputtering The copper layer (second current collector) 3 was placed on the polymer insulating layer 7 and the negative electrode material layer 6, and then encapsulated with an epoxy resin to obtain a self-charging lithium ion battery sample 1#. The sample 1# was placed in an ultrasonic wave of 1 Hz for 2 minutes, and after taking out, a discharge test was performed, and a constant current discharge was performed at 0.02 mA, and the discharge capacity of the sample 1# was 2.3 mAh. Example 2
本实施例自充电锂离子电池的整体尺寸为 40x60mm。 采用纯度 99.5%厚 度 ΙΟμηι的铝箔作为第一集电器 1 , 采用 ΙΟμηι的射频溅镀铜层作为第二集电 器 3。 多个氧化辞纳米线阵列 2生长在第一集电器 1上， 氧化辞纳米线的长 度为 20μηι。 压电纳米线阵列 2之间存在分隔间隙， 每个压电纳米线阵列 2 的尺寸为 3mmx40mm, 分隔间隙的尺寸为宽度为 5mmx40mm; 所述压电纳 米线阵列 2上覆盖有所述高分子绝缘层（聚曱基丙烯酸曱酯层） 7。 第二集电 器 3覆盖在高分子绝缘层 7上。 The overall size of the self-charging lithium ion battery of this embodiment is 40 x 60 mm. An aluminum foil having a purity of 99.5% thick ΙΟμηι was used as the first current collector 1 , and an RF sputtering copper layer of ΙΟμηι was used as the second current collector 3. A plurality of oxidized nanowire arrays 2 are grown on the first current collector 1, and the length of the oxidized nanowires is 20 μm. There is a separation gap between the piezoelectric nanowire arrays 2, each of the piezoelectric nanowire arrays 2 has a size of 3 mm×40 mm, and a size of the separation gap is 5 mm×40 mm; the piezoelectric nanowire array 2 is covered with the polymer insulation. Layer (poly(decyl acrylate) layer) 7. The second collector 3 is covered on the polymer insulating layer 7.
负极材料层 6的活性材料为石墨。 正极材料层 4的活性材料为锰酸锂。 采用常规单层聚丙烯微孔膜（PP )作为聚合物隔膜 5。 采用以 lmol/L的浓度 溶解了 LiPF6的碳酸亚乙酯溶液作为电解质。 正极材料层 4, 聚合物隔膜 5和 负极材料层 6依次间隔的设置在压电纳米线阵列 2的分隔间隙中， 且正极材 料层 4和第一集电器 1连接， 负极材料层 6与第二集电器 3连接。 在正极材 料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料层 6之间填充电解质 （图 未示）。 The active material of the negative electrode material layer 6 is graphite. The active material of the positive electrode material layer 4 is lithium manganate. A conventional single-layer polypropylene microporous membrane (PP) was used as the polymer membrane 5. An ethylene carbonate solution in which LiPF 6 was dissolved at a concentration of 1 mol/L was used as an electrolyte. The positive electrode material layer 4, the polymer separator 5 and the negative electrode material layer 6 are sequentially spaced apart in the separation gap of the piezoelectric nanowire array 2, and the positive electrode material layer 4 is connected to the first current collector 1, and the negative electrode material layer 6 and the second Collector 3 is connected. An electrolyte (not shown) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6.
下面说明本实施例自充电锂离子电池的制备方法。 The preparation method of the self-charging lithium ion battery of this embodiment will be described below.
用常规喷射溅镀在用作第一集电器 1的铝箔的一个面上生成厚度 lOOnm 的氧化辞种子层。 在氧化辞种子层上覆盖常规光阻材料， 用微加工平板印刷 法在光阻材料上开一个个规则的方形窗阵列， 方形窗口内区域， 棵露有氧化 辞种子， 方形窗口内区域生长压电纳米线阵列 2 , 方形窗口间隙存在光阻材 料而使氧化辞纳米线无法生长。 光阻材料在随后的氧化辞纳米线生长过程中 相当于一个分区模具，使氧化辞纳米线只生长在有暴露氧化辞种子的区域内， 从而实现氧化辞纳米线阵列 2间存在空隙。 具体的氧化辞纳米线的生长方法 如下： 采用 O. lmol/L浓度的由等摩尔的环六亚曱基四胺（HMTA )和硝酸辞 六水合物（ZnN03.6(H20) )组成的培养液， 将铝箔的生成有氧化辞种子层的
面朝下， 放在培养液顶部， 在 85 °C下在机械对流加热炉 （型号： Yamato DKN400, 加利福尼亚， 圣克拉拉） 中生长 20小时。 用去离子水沖洗生长有 氧化辞纳米线的铝箔并在空气中干燥。 然后剥落所有剩余光阻材料， 并对纳 米线阵列在 150°C加热退火。 然后通过旋涂将高分子绝缘层（聚曱基丙烯酸 曱酯层）涂覆于氧化辞纳米线阵列 2上。 An oxidized seed layer having a thickness of 100 nm was formed on one face of the aluminum foil used as the first current collector 1 by conventional spray sputtering. The conventional photoresist material is covered on the oxidized seed layer, and a regular square window array is opened on the photoresist material by micro-processing lithography. The inner area of the square window is exposed with oxidized seeds, and the growth pressure in the square window is increased. In the electric nanowire array 2, a photoresist material exists in the square window gap to make the oxidized nanowires unable to grow. The photoresist material is equivalent to a zoned mold during the subsequent oxidation of the nanowires, so that the oxidized nanowires are only grown in the region where the exposed oxidized seeds are present, thereby realizing the presence of voids between the oxidized nanowire arrays 2. The specific oxidation method of the nanowires is as follows: using an equimolar amount of cyclohexamethylenetetramine (HMTA) and nitric acid hexahydrate (ZnN0 3 .6 (H 2 0)) at a concentration of 0.1 mol/L The composition of the culture solution, the formation of the aluminum foil has an oxidized seed layer Face down, placed on top of the culture medium and grown at 85 °C for 20 hours in a mechanical convection oven (Model: Yamato DKN400, Santa Clara, Calif.). The aluminum foil grown with the oxidized nanowires was rinsed with deionized water and dried in air. All remaining photoresist material was then peeled off and the nanowire array was annealed at 150 °C. Then, a polymer insulating layer (polydecyl acrylate layer) was applied onto the oxidized nanowire array 2 by spin coating.
将锰酸锂、 碳黑、 聚偏二氟乙烯按照质量比为 86: 11 : 3混合。 然后将 上述混合物与 NMP (曱基吡咯烷酮 )混合， 得到固体成分为 20%的材料层用 浆料。 按照材料层的干燥质量为 15mg/cm2, 将浆料均匀地涂布在第一集电器 1面上的压电纳米线阵列 2的分隔间隙中。 接着， 在 50°C下干燥 5分钟， 形 成正极材料层 4。 在压电纳米线阵列 2的分隔间隙中， 相对正极材料层 4间 隔的放置聚合物隔膜 5。 Lithium manganate, carbon black, and polyvinylidene fluoride were mixed at a mass ratio of 86:11:3. Then, the above mixture was mixed with NMP (mercaptopyrrolidone) to obtain a slurry for a material layer having a solid content of 20%. The slurry was uniformly coated in the separation gap of the piezoelectric nanowire array 2 on the surface of the first current collector 1 in accordance with the dry mass of the material layer of 15 mg/cm 2 . Next, it was dried at 50 ° C for 5 minutes to form a positive electrode material layer 4 . In the separation gap of the piezoelectric nanowire array 2, the polymer separator 5 is placed spaced apart from the positive electrode material layer 4.
将石墨（平均粒径 20 μ m )和乙醇混合， 得到固体成分为 20质量％的负 极材料层用浆料。 相对聚合物隔膜间隔的， 在压电纳米线阵列 2的分隔间隙 中涂布负极材料层浆料。 浆料的涂布量为了使材料层的干燥质量达到 15mg/cm2。 在 50°C的温度下干燥处理 15分钟， 将溶剂除去， 得到负极材料 层 6。 Graphite (average particle diameter: 20 μm) and ethanol were mixed to obtain a slurry for a negative electrode material layer having a solid content of 20% by mass. The anode material layer slurry is applied in the separation gap of the piezoelectric nanowire array 2 with respect to the polymer separator. The coating amount of the slurry to the dry mass of the material layer reaches the 15mg / cm 2. The mixture was dried at a temperature of 50 ° C for 15 minutes, and the solvent was removed to obtain a negative electrode material layer 6.
在正极材料层 4与聚合物隔膜 5、 聚合物隔膜 5与负极材料层 6之间填 充电解质（以 lmol/L的浓度溶解了 LiPF6的碳酸亚乙酯溶液）（图未示 ), 然 后利用射频溅镀将铜层（第二集电器） 3设置到高分子绝缘层 7和负极材料 层 6上， 然后用环氧基树脂封装， 得到自充电锂离子电池样品 2#。 An electrolyte (a solution of ethylene carbonate in which LiPF6 is dissolved at a concentration of 1 mol/L) is filled between the positive electrode material layer 4 and the polymer separator 5, the polymer separator 5, and the negative electrode material layer 6 (not shown), and then the radio frequency is utilized. The copper layer (second current collector) 3 was placed on the polymer insulating layer 7 and the negative electrode material layer 6 by sputtering, and then encapsulated with an epoxy resin to obtain a self-charging lithium ion battery sample 2#.
将样品 2#放在 1Hz的超声波中持续 10分钟， 取出后， 进行放电测试， 以 0.02mA进行恒定电流放电， 样品 1#的放电容量为 1.9mAh。 The sample 2# was placed in an ultrasonic wave of 1 Hz for 10 minutes, and after taking out, a discharge test was performed, and a constant current discharge was performed at 0.02 mA, and the discharge capacity of the sample 1# was 1.9 mAh.
本发明的自充电锂离子电池， 采用以压电纳米材料阵列为基础的纳米发 电机进行发电。 由于该纳米发电机具有高能量转换效率， 从而在压力或超声 波作用下， 能够将锂离子从正极移动到负极并嵌入。 本发明自充电锂离子电 池与常规锂离子电池具有相同的应用领域， 例如手机、 无线信号接收发射等 电子产品。 本发明自充电锂离子电池特别适用于外部电源匮乏的场合。
The self-charging lithium ion battery of the present invention uses a nano-generator based on a piezoelectric nanomaterial array for power generation. Since the nanogenerator has high energy conversion efficiency, lithium ions can be moved from the positive electrode to the negative electrode and embedded under the action of pressure or ultrasonic waves. The self-charging lithium ion battery of the present invention has the same application fields as conventional lithium ion batteries, such as mobile phones, wireless signal receiving and transmitting, and the like. The self-charging lithium ion battery of the present invention is particularly suitable for applications where external power is scarce.
Claims
1. 一种自充电锂离子电池， 其特征在于， 包括第一集电器 (1), 压电纳米 线阵列 (2), 第二集电器 (3), 正极材料层 (4), 聚合物隔膜 (5), 负极材料层 (6), 电解质， 以及高分子绝缘层 (7); A self-charging lithium ion battery, comprising: a first current collector (1), a piezoelectric nanowire array ( 2 ), a second current collector (3), a positive electrode material layer ( 4 ), a polymer separator (5), a negative electrode material layer (6), an electrolyte, and a polymer insulating layer (7);
其中， 第一集电器 (1)与第二集电器 (3)平行放置； Wherein the first current collector (1) is placed in parallel with the second current collector (3);
多个压电纳米线阵列 (2)横跨第一集电器 (1)和第二集电器 (3)设置在第一 集电器 (1)与第二集电器 (3)之间， 且压电纳米线阵列 (2)相互之间存在分隔间 隙； 所述压电纳米线阵列 (2)上覆盖有所述高分子绝缘层 (7)； a plurality of piezoelectric nanowire arrays (2) disposed between the first current collector (1) and the second current collector (3) across the first current collector (1) and the second current collector (3), and piezoelectric The nanowire array (2) has a separation gap between each other; the piezoelectric nanowire array (2) is covered with the polymer insulation layer (7);
正极材料层 (4) ,聚合物隔膜 (5)和负极材料层 (6)依次间隔设置在压电纳米 线阵列 (2)的分隔间隙中，且正极材料层 (4)或负极材料层 (6)分别与第一集电器 (1)或第二集电器 (3)连接； 以及 The positive electrode material layer (4), the polymer separator (5) and the negative electrode material layer (6) are sequentially disposed in the separation gap of the piezoelectric nanowire array (2), and the positive electrode material layer (4) or the negative electrode material layer (6) ) are respectively connected to the first current collector (1) or the second current collector (3); and
分别在正极材料层 (4)与聚合物隔膜 (5)、 聚合物隔膜 (5)与负极材料层 (6) 之间填充电解质。 An electrolyte is filled between the positive electrode material layer (4) and the polymer separator (5), the polymer separator (5), and the negative electrode material layer (6), respectively.
2. 根据权利要求 1所述的自充电锂离子电池， 其特征在于， 所述第一集 电器 (1)和第二集电器 (3)所用材料分别独立的选自铝、 铜、 镍、 聚苯胺、 聚乙 炔、 聚吡咯、 聚噻吩、 聚对位亚苯基或聚苯乙炔。 2. The self-charging lithium ion battery according to claim 1, wherein the materials used by the first current collector (1) and the second current collector (3) are independently selected from the group consisting of aluminum, copper, nickel, and poly. Aniline, polyacetylene, polypyrrole, polythiophene, polyparaphenylene or polyphenylacetylene.
3. 根据权利要求 1或 2所述的自充电锂离子电池， 其特征在于， 所述压 电材料是氧化辞纳米线、 锆钛酸铝纳米线或钛酸钡纳米线。 The self-charging lithium ion battery according to claim 1 or 2, wherein the piezoelectric material is an oxidized nanowire, an aluminum zirconate titanate nanowire or a barium titanate nanowire.
4. 根据权利要求 3所述的自充电锂离子电池， 其特征在于， 所述高分子 绝缘层（7 )所用材料是聚曱基丙烯酸曱酯或聚二曱基硅氧烷。 The self-charging lithium ion battery according to claim 3, wherein the material of the polymer insulating layer (7) is polydecyl acrylate or polydithiosiloxane.
5. 根据权利要求 1-4任一项所述的自充电锂离子电池， 其特征在于， 所 述负极材料层 (6)中所用活性材料是石墨， 碳纳米管或碳纤维。 The self-charging lithium ion battery according to any one of claims 1 to 4, wherein the active material used in the anode material layer (6) is graphite, carbon nanotubes or carbon fibers.
6. 根据权利要求 1-5任一项所述的自充电锂离子电池， 其特征在于， 所 述正极材料层（4)中所用活性材料是锰酸锂、 磷酸铁锂、 钴酸锂或 The self-charging lithium ion battery according to any one of claims 1 to 5, wherein the active material used in the positive electrode material layer (4) is lithium manganate, lithium iron phosphate, lithium cobalt oxide or
Li-Ni-Co-Mn-0三元正极材料。 Li-Ni-Co-Mn-0 ternary cathode material.
7. 根据权利要求 1-6任一项所述的自充电锂离子电池， 其特征在于， 以 井字分割、 米字分割或斑马线分割的分隔方式， 形成多个相互之间存在分隔
间隙的压电纳米线阵列（2)。
The self-charging lithium ion battery according to any one of claims 1 to 6, wherein a plurality of separations are formed by a division method of a well word division, a rice word division or a zebra line division. Interstitial piezoelectric nanowire array (2).
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| CN201210254623.2A CN103579707B (en) | 2012-07-20 | 2012-07-20 | Self-charging lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3192163B1 (en) * | 2014-09-08 | 2020-06-24 | Nokia Technologies Oy | Flexible, hybrid energy generating and storage power cell |
| CN114551970A (en) * | 2021-11-17 | 2022-05-27 | 万向一二三股份公司 | Self-charging type all-solid-state battery |
| DE102022208174A1 (en) | 2022-08-05 | 2024-02-08 | Volkswagen Aktiengesellschaft | Process for producing lithium-ion battery cells |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9761861B1 (en) | 2013-06-25 | 2017-09-12 | Quantumscape Corporation | Pulse plating of lithium material in electrochemical devices |
| US10700377B2 (en) | 2017-01-17 | 2020-06-30 | Samsung Electronics Co., Ltd. | Solid electrolyte for a negative electrode of a secondary battery including first and second solid electrolytes with different affinities for metal deposition electronchemical cell and method of manufacturing |
| US11735780B2 (en) | 2017-03-10 | 2023-08-22 | Quantumscape Battery, Inc. | Metal negative electrode ultrasonic charging |
| CN106876660A (en) * | 2017-03-24 | 2017-06-20 | 江苏乐能电池股份有限公司 | A kind of lithium ion battery piezoelectricity positive pole composite pole piece and its lithium ion battery applications |
| US10840513B2 (en) | 2018-03-05 | 2020-11-17 | Samsung Electronics Co., Ltd. | Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell |
| CN111916710A (en) * | 2020-08-17 | 2020-11-10 | 中国科学院宁波材料技术与工程研究所 | Composite lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN112018457A (en) * | 2020-09-04 | 2020-12-01 | 南开大学 | Chemical self-charging battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090115293A1 (en) * | 2005-12-20 | 2009-05-07 | Georgia Tech Research Corporation | Stacked Mechanical Nanogenerators |
| US20100007248A1 (en) * | 2004-06-14 | 2010-01-14 | Massachusetts Institute Of Technology | Electrochemical methods, devices, and structures |
| US20100033059A1 (en) * | 2008-08-07 | 2010-02-11 | Samsung Electronics Co., Ltd. | Apparatus for generating electrical energy and method for manufacturing the same |
| US20100141095A1 (en) * | 2008-12-08 | 2010-06-10 | Electronics And Telecommunications Research Institute | Nano piezoelectric device and method of forming the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378551A (en) * | 1993-07-19 | 1995-01-03 | Motorola, Inc. | Rechargeable battery cell having integral vibrating means |
| JP3830243B2 (en) * | 1997-10-06 | 2006-10-04 | トヨタ自動車株式会社 | Battery power supply |
| JP2010518578A (en) * | 2007-02-09 | 2010-05-27 | シンベット・コーポレイション | Charging system and charging method |
-
2012
- 2012-07-20 CN CN201210254623.2A patent/CN103579707B/en active Active
-
2013
- 2013-03-15 WO PCT/CN2013/072685 patent/WO2014012379A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100007248A1 (en) * | 2004-06-14 | 2010-01-14 | Massachusetts Institute Of Technology | Electrochemical methods, devices, and structures |
| US20090115293A1 (en) * | 2005-12-20 | 2009-05-07 | Georgia Tech Research Corporation | Stacked Mechanical Nanogenerators |
| US20100033059A1 (en) * | 2008-08-07 | 2010-02-11 | Samsung Electronics Co., Ltd. | Apparatus for generating electrical energy and method for manufacturing the same |
| US20100141095A1 (en) * | 2008-12-08 | 2010-06-10 | Electronics And Telecommunications Research Institute | Nano piezoelectric device and method of forming the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3192163B1 (en) * | 2014-09-08 | 2020-06-24 | Nokia Technologies Oy | Flexible, hybrid energy generating and storage power cell |
| CN114551970A (en) * | 2021-11-17 | 2022-05-27 | 万向一二三股份公司 | Self-charging type all-solid-state battery |
| CN114551970B (en) * | 2021-11-17 | 2023-08-15 | 万向一二三股份公司 | Self-charging all-solid-state battery |
| DE102022208174A1 (en) | 2022-08-05 | 2024-02-08 | Volkswagen Aktiengesellschaft | Process for producing lithium-ion battery cells |
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