WO2022143159A1 - Lithium-ion microelectrode battery and preparation method therefor - Google Patents
Lithium-ion microelectrode battery and preparation method therefor Download PDFInfo
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- WO2022143159A1 WO2022143159A1 PCT/CN2021/137955 CN2021137955W WO2022143159A1 WO 2022143159 A1 WO2022143159 A1 WO 2022143159A1 CN 2021137955 W CN2021137955 W CN 2021137955W WO 2022143159 A1 WO2022143159 A1 WO 2022143159A1
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- quartz glass
- glass tube
- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000000084 colloidal system Substances 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004831 Hot glue Substances 0.000 claims description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 3
- 230000004323 axial length Effects 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
Definitions
- the invention relates to the technical field of micro-electrode preparation, in particular to a lithium-ion micro-electrode battery and a preparation method thereof.
- the traditional button battery is the main carrier for lithium-ion battery testing in the laboratory at present, but in the electrochemical test of microelectrodes, the traditional button battery has the following two shortcomings: Compared with the microelectrode, the volume of the traditional button battery Larger, more electrolyte is used in battery assembly, which directly leads to a large polarization reaction of the microelectrode during the charging and discharging process, and even when the traditional button type is used as the carrier, the electrochemical performance of the microelectrode cannot be measured at all; traditional The button battery must be pressed by a press when it is sealed, and for the microelectrode, the microelectrode particles will be crushed during the pressing process, which will directly lead to the failure of the battery.
- the purpose of the present invention is to provide a lithium ion microelectrode battery and a preparation method thereof, so as to solve the problems raised in the above background technology.
- a first aspect of the present invention discloses a preparation method of a lithium ion microelectrode battery, comprising the following steps:
- the molten lithium is sucked into the quartz glass tube by the pipette, the molten lithium fixes the copper wire inside the quartz glass tube, and the opening of one end of the quartz glass tube is closed by colloid;
- the lengths of the quartz glass tube and the short PVC tube are both 1.5-2 cm.
- a pipette with a capacity of 1 ml is used to collect the molten lithium, and the tip of the pipette is inserted into the other end of the PVC hose, so that the molten lithium is sucked into the quartz glass tube, and finally all the The region in the quartz glass tube with an axial length k is filled with lithium.
- the value of k is 1-1.5 cm.
- a platinum wire is provided on the microelectrode as a current collector.
- the microelectrodes include LiFePO 4 .
- the electrolyte includes LiclO 4 solution.
- a second aspect of the present invention discloses a lithium-ion microelectrode battery, comprising a quartz glass tube, lithium, copper wires, and an electrolyte, the lithium is filled in a first area in the quartz glass tube, and the electrolyte is filled in the In the second area in the quartz glass tube, one end of the copper wire is fixed in the first area by lithium, a micro-electrode is placed in the electrolyte, and a platinum wire is set on the micro-electrode as a current collector, so Both ends of the quartz glass tube are sealed by colloid.
- the preparation method of the lithium ion micro-electrode battery provided by the invention effectively reduces the polarization of the battery, so that the micro-electrode battery can be re-discharged normally; effectively avoids the breakage of electrode particles caused by the pressing process of the traditional button battery; and the total cost The cost is lower than the traditional button battery, and it can be prepared on a large scale in the laboratory;
- the invention also provides a lithium ion micro-electrode battery, which has small battery polarization, high coulombic efficiency, convenient preparation, low cost, and is convenient for large-scale preparation in the laboratory.
- FIG. 1 is a schematic diagram of a lithium ion microelectrode battery provided in Embodiment 6 of the present invention.
- FIG. 2 is a schematic diagram of a charge-discharge cycle curve (5 circles) of a lithium-ion microelectrode battery provided by the present invention
- FIG. 3 is a schematic diagram of the microelectrode charge-discharge Coulomb efficiency (5 cycles) of a lithium ion microelectrode battery provided by the present invention.
- a first aspect of the present invention discloses a preparation method of a lithium ion microelectrode battery, comprising the following steps:
- Step 101 Select a quartz glass tube with an outer diameter of 3 mm, an inner diameter of 0.4 mm, and a PVC hose with an outer diameter of 4 mm and an inner diameter of 2 mm, cut the above quartz glass tube and PVC hose into short tubes of 1.5-2.0 cm, and cleaning and drying;
- the battery structure can have a certain mechanical strength, which can effectively reduce the risk of the quartz glass tube being broken for some reason.
- a PVC hose with an inner diameter smaller than the outer diameter of the quartz glass tube can ensure the tightness of the connection. Due to the elasticity of the PVC hose, a quartz glass tube with an outer diameter of 3mm can be inserted into a PVC hose with an inner diameter of 2mm and Guaranteed good sealing.
- Step 102 insert one end of the quartz glass tube into the PVC hose, and insert a copper wire with a length of 4 cm and a thickness of 50 ⁇ m from the other end of the quartz glass tube as a wire;
- Step 103 Cut out a section of lithium tape in the glove box, place it in a stainless steel crucible and heat it to melt; insert the pipette tip (with a capacity of 1 ml) (with a tip inner diameter of 0.06-0.08 mm) into the other side of the PVC hose. At one end, the molten lithium is sucked into the quartz tube with a pipette, the molten lithium fixes the copper wire inside the quartz glass tube, and the opening of one end of the quartz glass tube is closed with colloid
- Step 104 Remove the PVC hose and inject the electrolyte (LiclO 4 solution) into the quartz glass tube, so that the electrolyte fills the remaining space of the quartz tube, so as to avoid air bubbles in the quartz tube causing the battery to be disconnected.
- the micro-electrode (LiFePO 4 ) with the wire as the current collector is put into a quartz glass tube, and the platinum wire is used as another wire.
- the opening of the other end of the quartz glass tube is closed, and finally the assembled quartz glass tube is wrapped with black insulating tape.
- Example 2 The difference between Example 2 and Example 1 is that the tip of the pipette is inserted into the other end of the PVC hose, so that the molten lithium is sucked into the quartz glass tube, and the tightness of the PVC hose can be ensured There is no gas leakage when the molten lithium is drawn into the quartz tube.
- the difference between the present embodiment 4 and the embodiment 1 is that the two openings of the quartz glass tube are sealed by hot melt adhesive to isolate the lithium from the air and avoid the reaction between the lithium and the air during the test.
- Example 5 The difference between Example 5 and Example 4 is that a sealing film is used to cover the opening at one end of the quartz glass tube for accommodating the electrolyte, and light-curing glue is used to seal the cover.
- the second aspect of the present invention discloses a lithium ion microelectrode battery, comprising a quartz glass tube 1 with a length of 1.5-2.2 cm, an outer diameter of 3 mm and an inner diameter of 0.4 mm, a lithium 2, a copper wire 3, an electrolyte solution 4 (LiclO4 solution), the lithium 2 is filled in the first area in the quartz glass tube 1, the electrolyte 4 is filled in the second area in the quartz glass tube 1, the copper wire 3 is One end is fixed in the first area by lithium 2, the other end of the copper wire 3 extends to the outside of the quartz glass tube 1 as a wire, the electrolyte 4 is placed with a microelectrode 5 (LiFePO4), and the microelectrode 5 (LiFePO4) is placed in the electrolyte 4.
- the electrode 5 is provided with a platinum wire 6 as a current collector, and the platinum wire 6 also extends to the outside of the quartz glass tube 1 as a wire, and both ends of the
- the length of the first region ranges from 1 to 1.5 cm.
- the colloid 7 includes one or more of hot melt adhesive and light curing adhesive.
- the electrochemical performance of the obtained lithium ion microelectrode battery was tested, and the results are shown in FIGS. 2 and 3 . It can be seen from the charge-discharge cycle curve and charge-discharge coulomb efficiency of the battery shown in Figures 2 and 3 that the battery structure can perform electrochemical tests on microelectrodes, and effectively reduce the polarization response of the battery, and Coulombic efficiency with batteries is higher.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Provided by the present invention are a lithium-ion microelectrode battery and a preparation method therefor. The preparation method comprises the following steps: selecting a quartz glass tube having an outer diameter of 3 mm and an inner diameter of 0.4 mm and a PVC hose having an outer diameter of 4 mm and an inner diameter of 2 mm, and performing cleaning and drying; inserting one end of the quartz glass tube into the PVC hose, selecting a certain length of copper wire, and placing the copper wire into the quartz glass tube; suctioning melted lithium into the quartz glass tube by using a pipette, fixing the copper wire at the interior of the quartz glass tube by using the melted lithium, and closing the opening at one end of the quartz glass tube by using a colloid; removing the PVC hose, injecting an electrolyte into the interior of the quartz glass tube, and simultaneously placing a microelectrode into the quartz glass tube; and closing the opening at the other end of the quartz glass tube by using a colloid, and finally wrapping the quartz glass tube by using black insulating tape.
Description
本发明涉及微电极制备技术领域，尤其涉及一种锂离子微电极电池及其制备方法。The invention relates to the technical field of micro-electrode preparation, in particular to a lithium-ion micro-electrode battery and a preparation method thereof.
传统的扣式电池是目前实验室进行锂离子电池测试的主要载体，但在微电极电化学测试方面，传统扣式电池有以下两点不足：相对于微电极而言，传统扣式电池的体积较大，在电池装配时所用电解液较多，直接导致微电极在充放电过程中产生很大的极化反应，甚至以传统扣式为载体时根本测不出微电极的电化学性能；传统扣式电池在密封时必须经过压力机压合，而对于微电极而言，在压合过程中会将微电极颗粒压破，直接导致电池失效。The traditional button battery is the main carrier for lithium-ion battery testing in the laboratory at present, but in the electrochemical test of microelectrodes, the traditional button battery has the following two shortcomings: Compared with the microelectrode, the volume of the traditional button battery Larger, more electrolyte is used in battery assembly, which directly leads to a large polarization reaction of the microelectrode during the charging and discharging process, and even when the traditional button type is used as the carrier, the electrochemical performance of the microelectrode cannot be measured at all; traditional The button battery must be pressed by a press when it is sealed, and for the microelectrode, the microelectrode particles will be crushed during the pressing process, which will directly lead to the failure of the battery.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种锂离子微电极电池及其制备方法，以解决上述背景技术中提出的问题。The purpose of the present invention is to provide a lithium ion microelectrode battery and a preparation method thereof, so as to solve the problems raised in the above background technology.
本发明是通过以下技术方案实现的：本发明第一方面公开了一种锂离子微电极电池的制备方法，包括下列步骤：The present invention is achieved through the following technical solutions: a first aspect of the present invention discloses a preparation method of a lithium ion microelectrode battery, comprising the following steps:
选取石英玻璃管以及PVC软管进行清洗烘干；Select quartz glass tubes and PVC hoses for cleaning and drying;
将所述石英玻璃管的一端塞入所述PVC软管内，选取铜丝，将铜丝放入石英玻璃管内；Insert one end of the quartz glass tube into the PVC hose, select copper wire, and put the copper wire into the quartz glass tube;
通过移液枪将烧融后的锂吸至石英玻璃管内，烧融后的锂将铜丝固定在石英玻璃管内部，并通过胶体将所述石英玻璃管的一端开口封闭；The molten lithium is sucked into the quartz glass tube by the pipette, the molten lithium fixes the copper wire inside the quartz glass tube, and the opening of one end of the quartz glass tube is closed by colloid;
取下PVC软管，将电解液注入石英玻璃管内部，同时将微电极放入石英玻 璃管中，通过胶体将所述石英玻璃管的另一端开口封闭，最终将石英玻璃管用黑色绝缘胶带包裹。Take down the PVC hose, inject the electrolyte into the inside of the quartz glass tube, put the microelectrode into the quartz glass tube at the same time, seal the opening of the other end of the quartz glass tube by colloid, and finally wrap the quartz glass tube with black insulating tape.
优选的，所述石英玻璃管以及所述PVC短管的长度均为1.5-2cm。Preferably, the lengths of the quartz glass tube and the short PVC tube are both 1.5-2 cm.
优选的，使用容量为1毫升的移液枪采集烧融的锂，将移液枪的枪头塞进PVC软管的另一端，使得烧融的锂被吸入所述石英玻璃管内，最终使所述石英玻璃管内轴向长度为k的区域被锂填充。Preferably, a pipette with a capacity of 1 ml is used to collect the molten lithium, and the tip of the pipette is inserted into the other end of the PVC hose, so that the molten lithium is sucked into the quartz glass tube, and finally all the The region in the quartz glass tube with an axial length k is filled with lithium.
优选的，所述k的取值为1-1.5cm。Preferably, the value of k is 1-1.5 cm.
优选的，所述微电极与所述锂之间存在间距。Preferably, there is a distance between the microelectrode and the lithium.
优选的，所述微电极上设有铂丝作为集流体。Preferably, a platinum wire is provided on the microelectrode as a current collector.
优选的，所述微电极包括LiFePO
4。
Preferably, the microelectrodes include LiFePO 4 .
优选的，所述电解液包括LiclO
4溶液。
Preferably, the electrolyte includes LiclO 4 solution.
本发明第二方面公开了一种锂离子微电极电池，包括石英玻璃管、锂、铜丝、电解液，所述锂填充于所述石英玻璃管内的第一区域，所述电解液填充于所述石英玻璃管内的第二区域，所述铜丝的一端被锂固定于所述第一区域内，所述电解液中放置有微电极，所述微电极上设有铂丝作为集流体，所述石英玻璃管的两端通过胶体封口。A second aspect of the present invention discloses a lithium-ion microelectrode battery, comprising a quartz glass tube, lithium, copper wires, and an electrolyte, the lithium is filled in a first area in the quartz glass tube, and the electrolyte is filled in the In the second area in the quartz glass tube, one end of the copper wire is fixed in the first area by lithium, a micro-electrode is placed in the electrolyte, and a platinum wire is set on the micro-electrode as a current collector, so Both ends of the quartz glass tube are sealed by colloid.
与现有技术相比，本发明达到的有益效果如下：Compared with the prior art, the beneficial effects achieved by the present invention are as follows:
本发明提供的锂离子微电极电池的制备方法，有效降低了电池极化，使微电极电池能够正常的重放电；有效避免了传统扣式电池压合过程中造成的电极颗粒破碎；且总成本低于传统扣式电池的成本，能够在实验室大规模制备；The preparation method of the lithium ion micro-electrode battery provided by the invention effectively reduces the polarization of the battery, so that the micro-electrode battery can be re-discharged normally; effectively avoids the breakage of electrode particles caused by the pressing process of the traditional button battery; and the total cost The cost is lower than the traditional button battery, and it can be prepared on a large scale in the laboratory;
本发明还提供了一种锂离子微电极电池，其电池极化小，库伦效率高，并且制备方便，成本较低，便于实验室大规模制备。The invention also provides a lithium ion micro-electrode battery, which has small battery polarization, high coulombic efficiency, convenient preparation, low cost, and is convenient for large-scale preparation in the laboratory.
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所 需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的优选实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only preferred embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative labor.
图1为本发明实施例6提供的一种锂离子微电极电池的示意图。FIG. 1 is a schematic diagram of a lithium ion microelectrode battery provided in Embodiment 6 of the present invention.
图2为本发明提供的一种锂离子微电极电池的充放电循环曲线(5圈)示意图；2 is a schematic diagram of a charge-discharge cycle curve (5 circles) of a lithium-ion microelectrode battery provided by the present invention;
图3为本发明提供的一种锂离子微电极电池的微电极充放电库伦效率(5圈)示意图。3 is a schematic diagram of the microelectrode charge-discharge Coulomb efficiency (5 cycles) of a lithium ion microelectrode battery provided by the present invention.
图中，1石英玻璃管，2锂，3铜丝，4电解液，5微电极，6铂丝，7胶体。In the figure, 1 quartz glass tube, 2 lithium, 3 copper wire, 4 electrolyte, 5 microelectrode, 6 platinum wire, 7 colloid.
为了更好理解本发明技术内容，下面提供具体实施例，并结合附图对本发明做进一步的说明。In order to better understand the technical content of the present invention, specific embodiments are provided below, and the present invention is further described with reference to the accompanying drawings.
实施例1Example 1
本发明第一方面公开了一种锂离子微电极电池的制备方法，包括下列步骤：A first aspect of the present invention discloses a preparation method of a lithium ion microelectrode battery, comprising the following steps:
步骤101：对选取外径为3mm、内径为0.4mm石英玻璃管以及外径为4mm、内径为2mm的PVC软管，将上述石英玻璃管、PVC软管截断为1.5～2.0cm的短管，并进行清洗烘干；Step 101: Select a quartz glass tube with an outer diameter of 3 mm, an inner diameter of 0.4 mm, and a PVC hose with an outer diameter of 4 mm and an inner diameter of 2 mm, cut the above quartz glass tube and PVC hose into short tubes of 1.5-2.0 cm, and cleaning and drying;
通过使用外径为3mm,内径为0.4mm的石英玻璃管，可使电池结构具有一定的力学强度，可有效降低石英玻璃管因故破碎的风险。By using a quartz glass tube with an outer diameter of 3 mm and an inner diameter of 0.4 mm, the battery structure can have a certain mechanical strength, which can effectively reduce the risk of the quartz glass tube being broken for some reason.
采用内径比石英玻璃管外径小的PVC软管可确保连接处的密封性，由于PVC软管有弹性，因此可以将外径为3mm的石英玻璃管塞进内径为2mm的PVC软管中并保证良好的密封性。The use of a PVC hose with an inner diameter smaller than the outer diameter of the quartz glass tube can ensure the tightness of the connection. Due to the elasticity of the PVC hose, a quartz glass tube with an outer diameter of 3mm can be inserted into a PVC hose with an inner diameter of 2mm and Guaranteed good sealing.
步骤102：将所述石英玻璃管的一端塞入所述PVC软管内，将长为4cm，粗50μm的铜丝从石英玻璃管的另一端塞入作为导线；Step 102: insert one end of the quartz glass tube into the PVC hose, and insert a copper wire with a length of 4 cm and a thickness of 50 μm from the other end of the quartz glass tube as a wire;
步骤103：在手套箱中裁取一段锂带，置于不锈钢坩埚中加热至熔融；将移液枪(容量为1毫升)枪头(枪头内径0.06～0.08mm)塞进PVC软管的另一端，用移液枪将熔融的锂吸入石英管内，融化状态的锂将铜丝固定在石英玻璃管内部，并用胶体将所述石英玻璃管的一端开口封闭Step 103: Cut out a section of lithium tape in the glove box, place it in a stainless steel crucible and heat it to melt; insert the pipette tip (with a capacity of 1 ml) (with a tip inner diameter of 0.06-0.08 mm) into the other side of the PVC hose. At one end, the molten lithium is sucked into the quartz tube with a pipette, the molten lithium fixes the copper wire inside the quartz glass tube, and the opening of one end of the quartz glass tube is closed with colloid
步骤104：取下PVC软管，将电解液(LiclO
4溶液)注入石英玻璃管内部，使电解液填满石英管的剩余空间，可避免石英管内有气泡导致电池内断路，同时将设有铂丝作为集流体的微电极(LiFePO
4)上放入石英玻璃管中，其铂丝作为另一导线，为了避免电池内短路，其微电极与所述锂之间存在一定间距，通过胶体将所述石英玻璃管的另一端开口封闭，最终将组装完成的石英玻璃管用黑色绝缘胶带包裹。
Step 104: Remove the PVC hose and inject the electrolyte (LiclO 4 solution) into the quartz glass tube, so that the electrolyte fills the remaining space of the quartz tube, so as to avoid air bubbles in the quartz tube causing the battery to be disconnected. The micro-electrode (LiFePO 4 ) with the wire as the current collector is put into a quartz glass tube, and the platinum wire is used as another wire. The opening of the other end of the quartz glass tube is closed, and finally the assembled quartz glass tube is wrapped with black insulating tape.
实施例2Example 2
本实施例2与实施例1的区别在于，将移液枪的枪头塞进PVC软管的另一端，使得烧融的锂被吸入所述石英玻璃管内，通过PVC软管的密封性可以保证把熔融的锂吸入石英管内时不会漏气。The difference between Example 2 and Example 1 is that the tip of the pipette is inserted into the other end of the PVC hose, so that the molten lithium is sucked into the quartz glass tube, and the tightness of the PVC hose can be ensured There is no gas leakage when the molten lithium is drawn into the quartz tube.
实施例3Example 3
本实施例3与实施例1的区别在于，烧融的锂注入所述石英玻璃管内，最终使所述石英玻璃管内轴向长度为k的区域被锂填充，在填充过程中，铜丝的一个端部被锂完全包裹，使得铜丝不与电解液相接触，避免电池中形成小电容，影响微电极电化学测试。其中k区域的最大长度范围应当小于石英玻璃管的长度，在本实施例中所述k的取值为1-1.5cm。The difference between this embodiment 3 and embodiment 1 is that the molten lithium is injected into the quartz glass tube, and finally the area with the axial length k in the quartz glass tube is filled with lithium. During the filling process, one of the copper wires The end is completely wrapped with lithium, so that the copper wire is not in contact with the electrolyte, which avoids the formation of small capacitance in the battery and affects the electrochemical test of the micro-electrode. The maximum length range of the k region should be smaller than the length of the quartz glass tube, and the value of k in this embodiment is 1-1.5 cm.
实施例4Example 4
本实施例4与实施例1的区别在于，通过热熔胶对石英玻璃管的两个开口进行封闭，使锂与空气隔绝，避免测试过程中锂与空气反应。The difference between the present embodiment 4 and the embodiment 1 is that the two openings of the quartz glass tube are sealed by hot melt adhesive to isolate the lithium from the air and avoid the reaction between the lithium and the air during the test.
实施例5Example 5
本实施例5与实施例,4的区别在于，采用封口膜覆盖所述石英玻璃管中用 于容纳电解液的一端开口，在覆盖处使用光固化胶进行封口。The difference between Example 5 and Example 4 is that a sealing film is used to cover the opening at one end of the quartz glass tube for accommodating the electrolyte, and light-curing glue is used to seal the cover.
实施例6Example 6
参见图1，本发明第二方面公开了一种锂离子微电极电池，包括长度为1.5-2.2cm、外径为3mm、内径为0.4mm石英玻璃管1、锂2、铜丝3、电解液4(LiclO
4溶液)，所述锂2填充于所述石英玻璃管1内的第一区域，所述电解液4填充于所述石英玻璃管1内的第二区域，所述铜丝3的一端被锂2固定于所述第一区域内，所述铜丝3的另一端延伸至石英玻璃管1外部作为导线，所述电解液4中放置有微电极5(LiFePO
4)，所述微电极5上设有铂丝6作为集流体，所述铂丝6也延伸至石英玻璃管1外部作为导线，所述石英玻璃管1的两端通过胶体封口。
Referring to FIG. 1 , the second aspect of the present invention discloses a lithium ion microelectrode battery, comprising a quartz glass tube 1 with a length of 1.5-2.2 cm, an outer diameter of 3 mm and an inner diameter of 0.4 mm, a lithium 2, a copper wire 3, an electrolyte solution 4 (LiclO4 solution), the lithium 2 is filled in the first area in the quartz glass tube 1, the electrolyte 4 is filled in the second area in the quartz glass tube 1, the copper wire 3 is One end is fixed in the first area by lithium 2, the other end of the copper wire 3 extends to the outside of the quartz glass tube 1 as a wire, the electrolyte 4 is placed with a microelectrode 5 (LiFePO4), and the microelectrode 5 (LiFePO4) is placed in the electrolyte 4. The electrode 5 is provided with a platinum wire 6 as a current collector, and the platinum wire 6 also extends to the outside of the quartz glass tube 1 as a wire, and both ends of the quartz glass tube 1 are sealed by colloid.
具体的，所述第一区域的长度范围为1-1.5cm。Specifically, the length of the first region ranges from 1 to 1.5 cm.
具体的，所述胶体7包括热熔胶以及光固化胶中的一种或多种。Specifically, the colloid 7 includes one or more of hot melt adhesive and light curing adhesive.
将所得锂离子微电极电池进行电化学性能检测，结果见图2与图3。从图2与图3中显示的电池从充放放电循环曲线和充放电库伦效率中可以看出该电池结构能够对微电极进行电化学测试，且有效的降低了电池的极化法应，且带电池的库伦效率较高。The electrochemical performance of the obtained lithium ion microelectrode battery was tested, and the results are shown in FIGS. 2 and 3 . It can be seen from the charge-discharge cycle curve and charge-discharge coulomb efficiency of the battery shown in Figures 2 and 3 that the battery structure can perform electrochemical tests on microelectrodes, and effectively reduce the polarization response of the battery, and Coulombic efficiency with batteries is higher.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the present invention. within the scope of protection.
Claims (10)
- 一种锂离子微电极电池的制备方法，其特征在于，包括下列步骤：A preparation method of lithium ion microelectrode battery, characterized in that, comprising the following steps:选取石英玻璃管以及PVC软管进行清洗烘干；Select quartz glass tubes and PVC hoses for cleaning and drying;将所述石英玻璃管的一端塞入所述PVC软管内，选取铜丝，将铜丝放入石英玻璃管内；Insert one end of the quartz glass tube into the PVC hose, select copper wire, and put the copper wire into the quartz glass tube;通过移液枪将烧融后的锂吸至石英玻璃管内，烧融后的锂将铜丝固定在石英玻璃管内部，并通过胶体将所述石英玻璃管的一端开口封闭；The molten lithium is sucked into the quartz glass tube by the pipette, the molten lithium fixes the copper wire inside the quartz glass tube, and the opening of one end of the quartz glass tube is closed by colloid;取下PVC软管，将电解液注入石英玻璃管内部，同时将微电极放入石英玻璃管中，通过胶体将所述石英玻璃管的另一端开口封闭，最终将石英玻璃管用黑色绝缘胶带包裹。Remove the PVC hose, inject the electrolyte into the inside of the quartz glass tube, and put the microelectrode into the quartz glass tube at the same time, seal the opening of the other end of the quartz glass tube with colloid, and finally wrap the quartz glass tube with black insulating tape.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述石英玻璃管以及所述PVC短管的长度均为1.5-2cm。The method for preparing a lithium ion micro-electrode battery according to claim 1, wherein the lengths of the quartz glass tube and the short PVC tube are both 1.5-2 cm.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，使用容量为1毫升的移液枪采集烧融的锂，将移液枪的枪头塞进PVC软管的另一端，使得烧融的锂被吸入所述石英玻璃管内，最终使所述石英玻璃管内轴向长度为k的区域被锂填充。The method for preparing a lithium ion microelectrode battery according to claim 1, wherein the molten lithium is collected by a pipette with a capacity of 1 ml, and the tip of the pipette is inserted into the PVC hose. At the other end, the molten lithium is sucked into the quartz glass tube, and finally the region of the axial length k in the quartz glass tube is filled with lithium.
- 根据权利要求4所述的一种锂离子微电极电池的制备方法，其特征在于，所述k的取值为1-1.5cm。The method for preparing a lithium ion microelectrode battery according to claim 4, wherein the value of k is 1-1.5 cm.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述微电极与所述锂之间存在间距。The method for preparing a lithium-ion microelectrode battery according to claim 1, wherein a distance exists between the microelectrode and the lithium.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述微电极上设有铂丝作为集流体。The method for preparing a lithium-ion microelectrode battery according to claim 1, wherein a platinum wire is provided on the microelectrode as a current collector.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述微电极包括LiFePO 4。 The method for preparing a lithium-ion micro-electrode battery according to claim 1, wherein the micro-electrode comprises LiFePO 4 .
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述电解液包括LiclO 4溶液。 The method for preparing a lithium ion microelectrode battery according to claim 1, wherein the electrolyte comprises LiclO4 solution.
- 根据权利要求1所述的一种锂离子微电极电池的制备方法，其特征在于，所述胶体包括热熔胶以及光固化胶中的一种或多种。The method for preparing a lithium ion microelectrode battery according to claim 1, wherein the colloid comprises one or more of hot melt adhesive and light-curing adhesive.
- 一种根据权利要求1～9任一项所述的锂离子微电极电池的制备方法得到的锂离子微电极电池，其特征在于，包括石英玻璃管、锂、铜丝、电解液，所述锂填充于所述石英玻璃管内的第一区域，所述电解液填充于所述石英玻璃管内的第二区域，所述铜丝的一端被锂固定于所述第一区域内，所述电解液中放置有微电极，所述微电极上设有铂丝作为集流体，所述石英玻璃管的两端通过胶体封口。A lithium ion microelectrode battery obtained by the method for preparing a lithium ion microelectrode battery according to any one of claims 1 to 9, characterized in that it comprises a quartz glass tube, lithium, copper wire, and electrolyte, and the lithium The first area is filled in the quartz glass tube, the electrolyte is filled in the second area in the quartz glass tube, one end of the copper wire is fixed in the first area by lithium, and the electrolyte is in the first area. A micro-electrode is placed, a platinum wire is set on the micro-electrode as a current collector, and both ends of the quartz glass tube are sealed by colloid.
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