CN111965090B - A measuring device and characterization method for swelling properties of polymers for lithium batteries - Google Patents
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- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- 230000002522 swelling effect Effects 0.000 title claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 238000012512 characterization method Methods 0.000 title claims abstract description 13
- 230000008961 swelling Effects 0.000 claims abstract description 122
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000005259 measurement Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 9
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 206010042674 Swelling Diseases 0.000 description 90
- 239000000463 material Substances 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 11
- 238000013480 data collection Methods 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003292 glue Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
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- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N15/088—Investigating volume, surface area, size or distribution of pores; Porosimetry
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Abstract
本发明提供了一种锂电池用高聚物溶胀特性的测量装置,包括用以放置高聚物及溶剂的溶胀室,溶胀室内可移动的放置有钢网,钢网的顶部固定有导杆,溶胀室的进液口处塞有胶塞,胶塞上开有容导杆穿过的开孔,溶胀室的上方设有激光测距仪,胶塞上还开有容激光测距仪的激光穿过的通孔,还提供表征高聚物溶胀特性的方法,包括如下步骤:计算需加入的高聚物的质量及高聚物溶胀特性的表征。通过对体积的时时监测,数据采集处理系统将体积转化成溶胀表征值,形成时间、溶胀表征值的特性曲线,表征溶剂小分子进入高分子聚合物大分子颗粒中,使颗粒膨胀、分子链打开、舒展达到热力学稳定的二元均相体系的过程。
The invention provides a measuring device for the swelling characteristics of high polymers used in lithium batteries, including a swelling chamber for placing high polymers and solvents, a steel mesh is movable in the swelling chamber, and a guide rod is fixed on the top of the steel mesh. The liquid inlet of the swelling chamber is plugged with a rubber plug, and there is an opening for the guide rod to pass through on the rubber plug. A laser rangefinder is arranged above the swelling chamber, and a laser for the laser rangefinder is also opened on the rubber plug. The passing through holes also provide a method for characterizing the swelling properties of the high polymer, including the following steps: calculating the mass of the high polymer to be added and characterization of the swelling properties of the high polymer. Through the constant monitoring of the volume, the data acquisition and processing system converts the volume into a swelling characteristic value, and forms a characteristic curve of time and swelling characteristic value, indicating that the small solvent molecule enters the macromolecular polymer particle, causing the particle to expand and the molecular chain to open. , The process of stretching to reach a thermodynamically stable binary homogeneous system.
Description
技术领域technical field
本发明创造属于锂电池技术领域,尤其是涉及一种锂电池用高聚物溶胀特性的测量装置和表征方法。The invention belongs to the technical field of lithium batteries, and in particular relates to a measuring device and a characterization method for swelling properties of polymers used in lithium batteries.
背景技术Background technique
随着锂电、镍电在新能源领域的广泛应用,各大电池制造厂商在新技术、高品质、低成本、快速制造等方面竞争激烈,尤其在新材料开发初期物性的快速评价和量产后合理有效的生产工艺参数的制定等方面做着大量研究。With the widespread application of lithium batteries and nickel batteries in the field of new energy, major battery manufacturers compete fiercely in terms of new technology, high quality, low cost, and rapid manufacturing, especially in the rapid evaluation of physical properties in the initial stage of new material development and after mass production. A lot of research has been done on the formulation of reasonable and effective production process parameters.
CMC、PVDF、HPMC、PTFE、黄原胶等高分子聚合物是锂电、镍电常用的粘结剂,在电池中起到粘连活物颗粒、导电剂、集流体的作用,在保持电极的结构特性方面起到关键作用。使用时,将先高聚物粉末在溶剂中充分溶解,做成胶液。胶液与活性物质、导电剂等粉末混炼成浆料添加到电池中。高聚物在溶剂中的溶胀、溶解特性是胶液制作工艺的主要影响因素。High molecular polymers such as CMC, PVDF, HPMC, PTFE, and xanthan gum are commonly used binders for lithium batteries and nickel batteries. characteristics play a key role. When in use, fully dissolve the high polymer powder in a solvent to make a glue. The glue is mixed with active material, conductive agent and other powders to form a slurry and added to the battery. The swelling and dissolving characteristics of polymers in solvents are the main factors affecting the production process of glue.
高聚物在溶剂中形成均相分为溶胀、溶解两个过程,其中溶胀是溶剂小分子进入高聚物颗粒孔隙、高聚物颗粒膨胀、大分子链舒展、打开的过程。溶解是打开后的大分子和溶剂小分子形成二元均相的过程。新材料开发过程中,溶胀特性的掌握是开发、应用所必须的,对于新材料很好的应用于生产制造环节起到至关重要的作用。The formation of a homogeneous phase of a polymer in a solvent is divided into two processes: swelling and dissolution. The swelling is a process in which small solvent molecules enter the pores of polymer particles, polymer particles expand, and macromolecular chains stretch and open. Dissolution is a process in which the opened macromolecules and small solvent molecules form a binary homogeneous phase. In the development process of new materials, the mastery of swelling characteristics is necessary for development and application, and plays a vital role in the good application of new materials in the manufacturing process.
目前,行业内对锂离子电池用高聚物的溶胀、溶解特性的评价较为简单,没有形成统一的手法和标准,无法给出量化值,无法提供高聚物材料溶胀过程的量化值。At present, the evaluation of the swelling and dissolution characteristics of polymers for lithium-ion batteries is relatively simple in the industry. There is no unified method and standard, and it is impossible to give quantitative values, and it is impossible to provide quantitative values for the swelling process of polymer materials.
发明内容Contents of the invention
有鉴于此,本发明创造旨在提出一种锂电池用高聚物溶胀特性的测量装置和表征方法,以通过对体积的时时监测,数据采集处理系统将体积转化成溶胀表征值,形成时间、溶胀表征值的特性曲线,表征溶剂小分子进入高分子聚合物大分子颗粒中,使颗粒膨胀、分子链打开、舒展达到热力学稳定的二元均相体系的过程。In view of this, the present invention aims to propose a measuring device and characterization method for the swelling characteristics of polymers used in lithium batteries, so that the volume can be converted into a swelling characteristic value by the data acquisition and processing system through constant monitoring of the volume, forming time, The characteristic curve of the swelling characteristic value represents the process of small solvent molecules entering the polymer macromolecular particles to expand the particles, open the molecular chains, and stretch to achieve a thermodynamically stable binary homogeneous system.
为达到上述目的,本发明创造的技术方案是这样实现的:In order to achieve the above object, the technical solution created by the present invention is achieved in this way:
一种锂电池用高聚物溶胀特性的测量装置,包括用以放置高聚物及溶剂的溶胀室,溶胀室内可移动的放置有钢网,钢网的顶部固定有导杆,溶胀室的进液口处塞有胶塞,胶塞上开有容导杆穿过的开孔,溶胀室的上方设有激光测距仪,胶塞上还开有容激光测距仪的激光穿过的通孔。A measuring device for the swelling properties of high polymers used in lithium batteries, including a swelling chamber for placing high polymers and solvents, a steel mesh is movable in the swelling chamber, and a guide rod is fixed on the top of the steel mesh. The liquid port is plugged with a rubber plug, and the rubber plug has an opening for the guide rod to pass through. A laser rangefinder is arranged above the swelling chamber, and a hole for the laser rangefinder’s laser to pass through is also opened on the rubber plug. hole.
进一步的,还包括固定架,固定架的顶部向下开有放置所述溶胀室的凹槽。Further, it also includes a fixing frame, and the top of the fixing frame is downwardly opened with a groove for placing the swelling chamber.
进一步的,所述顶杆的顶部悬挂在所述胶塞的顶部。Further, the top of the ejector rod is suspended from the top of the rubber plug.
进一步的,还包括数据采集处理系统,所述激光测距仪与所述数据采集处理系统通过电信号连接。Further, a data collection and processing system is also included, and the laser distance meter is connected to the data collection and processing system through electrical signals.
一种表征高聚物溶胀特性的方法,包括如下步骤:A method for characterizing the swelling properties of polymers, comprising the steps of:
(1)计算需加入的高聚物的质量:(1) Calculate the mass of polymer to be added:
(A)量取用于溶解高聚物的溶剂,负压条件下静置除泡;(A) Measure the solvent used to dissolve the high polymer, and leave it to defoam under negative pressure;
进一步的,所述负压条件为真空度≤-90KPa。Further, the negative pressure condition is vacuum degree≤-90KPa.
(B)用激光测距仪测量激光测距仪到溶胀室底部的距离,记为H0;(B) measure the distance from the laser range finder to the bottom of the swelling chamber with a laser range finder, denoted as H 0 ;
进一步的,所述恒温的操作步骤在恒温槽中进行。Further, the operation step of constant temperature is carried out in a constant temperature bath.
进一步的,所述恒温槽的温度波动±0.05℃,数显分辩率为0.01℃,温度控制范围为0℃-90℃,容积优选为10L,加热介质优先为水。Further, the temperature fluctuation of the constant temperature tank is ±0.05°C, the digital display resolution is 0.01°C, the temperature control range is 0°C-90°C, the volume is preferably 10L, and the heating medium is preferably water.
(D)恒温完成后,激光测距仪测量步骤(3)中溶剂的液面顶部距离激光测距仪的距离,记为H1;(D) after the constant temperature is completed, the distance between the top of the liquid surface of the solvent and the laser range finder in the laser range finder measurement step (3) is denoted as H 1 ;
(E)根据如下公式计算溶胀室内溶剂的总体积V0:(E) Calculate the total volume V 0 of the solvent in the swelling chamber according to the following formula:
V0=(H1-H0)×(Φ/2)2×3.14,其中Φ为溶胀室的内径;V 0 =(H 1 -H 0 )×(Φ/2) 2 ×3.14, where Φ is the inner diameter of the swelling chamber;
(F)根据如下公式计算需加入溶胀室内的高聚物的质量W0;(F) Calculate the mass W 0 of the high polymer that needs to be added into the swelling chamber according to the following formula;
W0=V0/(1-α)×α,其中α为聚合物占溶胀后溶液的质量百分比;W 0 =V 0 /(1-α)×α, where α is the mass percentage of the polymer in the swollen solution;
计算时,常用溶剂的密度按照1g/cm3计算。When calculating, the density of common solvents is calculated according to 1g/cm 3 .
(2)高聚物溶胀特性的表征:(2) Characterization of polymer swelling properties:
(A)称量质量为W1的高聚物,其中W1=W0±0.0005g,将称量好的高聚物放入溶胀室中;(A) Weigh a high polymer with a mass of W 1 , wherein W 1 =W 0 ±0.0005g, and put the weighed high polymer into the swelling chamber;
进一步的,以有机溶剂作为高聚物的溶剂时,例如使用NMP、环已烷溶解PVDF时,胶塞主要耐腐蚀,胶塞的材质优选材质三元乙丙;以纯水作为高聚物溶剂时,例如用纯水测量CMC溶胀特性时,普通橡胶材质的胶塞即可。Further, when organic solvents are used as polymer solvents, for example, when NMP and cyclohexane are used to dissolve PVDF, the rubber plug is mainly corrosion-resistant, and the material of the rubber plug is preferably EPDM; pure water is used as the polymer solvent For example, when measuring the swelling properties of CMC with pure water, ordinary rubber plugs are sufficient.
(C)激光测距仪实时测量溶胀时间T及步骤(2)中(B)步骤中液面的顶部距离激光测距仪的距离H2,并根据如下公式计算溶胀过程中溶液的体积:V2=(H2-H0)×(Φ/2)2×3.14;(C) The laser range finder measures the swelling time T in real time and the distance H 2 from the top of the liquid surface in step (B) in step (2) to the laser range finder, and calculates the volume of the solution in the swelling process according to the following formula: V 2 =(H 2 -H 0 )×(Φ/2) 2 ×3.14;
(D)当溶胀表征值η不随溶胀时间T变化或变化很小时,停止测量,其中溶胀表征值η=V2/W1;绘制溶胀时间T和溶胀表征值η的关系曲线即为表征高聚物溶胀特性的曲线。(D) When the swelling characteristic value η does not change or changes very little with the swelling time T, stop the measurement, wherein the swelling characteristic value η=V 2 /W 1 ; draw the relationship curve between the swelling time T and the swelling characteristic value η to characterize the polymer The curve of the material swelling property.
进一步的,所述H2、H1、H0、Φ的单位均为mm,所述V2、V1的单位均为mL,所述W1、W0的单位均为g,所述η的单位为mL/g。Further, the units of H 2 , H 1 , H 0 , and Φ are mm, the units of V 2 and V 1 are mL, the units of W 1 and W 0 are g, and the η The unit is mL/g.
进一步的,步骤(1)中(C)步骤的恒温温度优选为20-25℃。Further, the constant temperature of step (C) in step (1) is preferably 20-25°C.
进一步的,所述溶胀室的内径值为5mm≤内径≤15mm,溶胀室的内径精度不低于±0.01mm,溶胀室的圆柱度不高于3um,溶胀室的表面粗糙度不低于0.8,溶胀室的高度值为100mm≤高度≤300mm。Further, the inner diameter of the swelling chamber is 5mm≤inner diameter≤15mm, the precision of the inner diameter of the swelling chamber is not less than ±0.01mm, the cylindricity of the swelling chamber is not higher than 3um, and the surface roughness of the swelling chamber is not lower than 0.8, The height value of the swelling chamber is 100mm≤height≤300mm.
进一步的,所述导杆的直径≤0.5mm,钢网开有孔径≤20um的网孔。Further, the diameter of the guide rod is ≤0.5mm, and the steel mesh has holes with a diameter of ≤20um.
进一步的,所述钢网的材质优选为sus304。Further, the material of the steel mesh is preferably sus304.
进一步的,使用天平称量高聚物的质量,天平精度为0.0001g。Further, a balance is used to weigh the mass of the polymer, and the precision of the balance is 0.0001 g.
进一步的,所述激光测距仪的测量精度为0.01mm,量程根据溶胀室的高度选择,激光测距仪优先的品牌为基恩士。Further, the measurement accuracy of the laser range finder is 0.01 mm, and the range is selected according to the height of the swelling chamber. The preferred brand of the laser range finder is KEYENCE.
进一步的,所述数据采集处理系统可自动读取激光测距仪输出的数据并记录,数据采集时间、频率、间隔可通过系统窗口设置,采集频率≥1个/5s;并且具有形成时时监控曲线的功能,便于操作人员查看;具有原始数据导出功能。Further, the data collection and processing system can automatically read and record the data output by the laser rangefinder, the data collection time, frequency, and interval can be set through the system window, and the collection frequency is ≥1/5s; and it has the ability to form a monitoring curve from time to time The function is convenient for operators to view; it has the function of exporting original data.
相对于现有技术,本发明创造所述的锂电池用高聚物溶胀特性的测量装置和表征方法具有以下优势:Compared with the prior art, the invention creates the measurement device and characterization method of the swelling properties of the polymer for lithium batteries and has the following advantages:
(1)本发明所述的锂电池用高聚物溶胀特性的测量装置和表征方法,通过对体积的时时监测,数据采集处理系统将体积转化成溶胀表征值,形成时间、溶胀表征值的特性曲线,表征溶剂小分子进入高分子聚合物大分子颗粒中,使颗粒膨胀、分子链打开、舒展达到热力学稳定的二元均相体系的过程。(1) The measurement device and characterization method for the swelling characteristics of polymers for lithium batteries according to the present invention, through the constant monitoring of the volume, the data acquisition and processing system converts the volume into swelling characteristic values, forming the characteristics of time and swelling characteristic values The curve represents the process of small solvent molecules entering the polymer macromolecular particles, making the particles swell, molecular chains open, and stretched to reach a thermodynamically stable binary homogeneous system.
(2)本发明所述的锂电池用高聚物溶胀特性的测量装置和表征方法,通过溶胀量化曲线,可快速掌握材料溶胀特性,有助于新材料快速应用于生产制造环节工艺参数的制定,新材料开发时,通过对新型号材料和现有型号量化特性曲线对比,快速掌握新型号材料高聚物溶胀、溶解特性,有助于快速制定合理生产工艺参数。(2) The measurement device and characterization method for the swelling characteristics of polymers for lithium batteries described in the present invention can quickly grasp the swelling characteristics of materials through the swelling quantification curve, which is helpful for the rapid application of new materials to the formulation of process parameters in the manufacturing process , When developing new materials, by comparing the quantitative characteristic curves of new materials and existing models, we can quickly grasp the swelling and dissolution characteristics of polymers of new materials, which will help to quickly formulate reasonable production process parameters.
(3)本发明所述的锂电池用高聚物溶胀特性的测量装置和表征方法,通过时间、溶胀表征值的特性曲线,将高聚物溶胀过程量化,提供一种测量高聚物溶胀特性的装置,通过溶胀过程中体积的变化,将溶胀过程量化,并给出量化曲线。(3) The measuring device and characterization method for the swelling characteristics of high polymers for lithium batteries according to the present invention, through the characteristic curves of time and swelling characterization values, quantify the swelling process of high polymers, and provide a method for measuring the swelling characteristics of high polymers The device quantifies the swelling process through the volume change in the swelling process and gives a quantitative curve.
附图说明Description of drawings
构成本发明创造的一部分的附图用来提供对本发明创造的进一步理解,本发明创造的示意性实施例及其说明用于解释本发明创造,并不构成对本发明创造的不当限定。在附图中:The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention, and the schematic embodiments and descriptions of the present invention are used to explain the present invention and do not constitute improper limitations to the present invention. In the attached picture:
图1为本发明创造实施例所述的测量装置的示意图;Fig. 1 is the schematic diagram of the measurement device described in the creation embodiment of the present invention;
图2为本发明创造说明书附图1中A的局部放大图;Fig. 2 is a partial enlarged view of A in the accompanying drawing 1 of the invention specification;
图3为本发明创造实施例所述的样品A的SEM形貌示意图;Fig. 3 is a schematic diagram of the SEM morphology of the sample A described in the inventive embodiment of the present invention;
图4为本发明创造实施例所述的样品B的SEM示意图;Fig. 4 is the SEM schematic diagram of the sample B described in the inventive embodiment of the present invention;
图5为本发明创造实施例所述的PVDF溶胀曲线示意图。Fig. 5 is a schematic diagram of the swelling curve of PVDF described in the inventive embodiment of the present invention.
附图标记说明:Explanation of reference signs:
1-高聚物粉末层;2-溶胀室;3-恒温槽;4-钢网;5-导杆;6-胶塞;7-固定架;8-激光测距仪;9-数据采集处理系统。1-polymer powder layer; 2-swelling chamber; 3-constant temperature tank; 4-steel mesh; 5-guide rod; 6-rubber plug; 7-fixing frame; system.
具体实施方式Detailed ways
需要说明的是,在不冲突的情况下,本发明创造中的实施例及实施例中的特征可以相互组合。It should be noted that, in the case of no conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.
在本发明创造的描述中,需要理解的是,术语“中心”、“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本发明创造和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明创造的限制。此外,术语“第一”、“第二”等仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”等的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明创造的描述中,除非另有说明,“多个”的含义是两个或两个以上。In describing the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", The orientations or positional relationships indicated by "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention Creation and simplification of description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and therefore should not be construed as limiting the invention. In addition, the terms "first", "second", etc. are used for descriptive purposes only, and should not be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, a feature defined as "first", "second", etc. may expressly or implicitly include one or more of that feature. In the description of the present invention, unless otherwise specified, "plurality" means two or more.
在本发明创造的描述中,需要说明的是,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。除非另有明确的规定和限定,术语“固定连接”可以是插接、焊接、螺纹连接、螺栓连接等常用的固定连接方式。对于本领域的普通技术人员而言,可以通过具体情况理解上述术语在本发明创造中的具体含义。In the description of the present invention, it should be noted that unless otherwise specified and limited, the terms "installation", "connection" and "connection" should be interpreted in a broad sense, for example, it can be a fixed connection or a flexible connection. Detachable connection, or integral connection; it can be mechanical connection or electrical connection; it can be direct connection or indirect connection through an intermediary, and it can be the internal communication of two components. Unless otherwise clearly specified and limited, the term "fixed connection" may refer to commonly used fixed connection methods such as plugging, welding, threaded connection, and bolted connection. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention based on specific situations.
下面将参考附图并结合实施例来详细说明本发明创造。The invention will be described in detail below with reference to the accompanying drawings and examples.
一种锂电池用高聚物溶胀特性的测量装置,包括用以放置高聚物及溶剂的溶胀室2,溶胀室2内可移动的放置有钢网4,钢网4的顶部固定有导杆5,溶胀室2的进液口处塞有胶塞6,胶塞6上开有容导杆5穿过的开孔,溶胀室2的上方设有激光测距仪8,胶塞6上还开有容激光测距仪8的激光穿过的通孔。A measuring device for the swelling properties of polymers used in lithium batteries, including a swelling chamber 2 for placing polymers and solvents, a steel mesh 4 is movable in the swelling chamber 2, and a guide rod is fixed on the top of the steel mesh 4 5. The liquid inlet of the swelling chamber 2 is plugged with a rubber plug 6, and the rubber plug 6 has an opening for the guide rod 5 to pass through. Have the through hole that the laser of laser rangefinder 8 passes through.
还包括固定架7,固定架7的顶部向下开有放置所述溶胀室2的凹槽。It also includes a fixing frame 7, and the top of the fixing frame 7 is downwardly opened with a groove for placing the swelling chamber 2.
实验过程中注意保持固定架7及溶胀室2的水平。During the experiment, pay attention to maintaining the level of the fixing frame 7 and the swelling chamber 2.
所述顶杆的顶部悬挂在所述胶塞6的顶部。The top of the push rod is suspended on the top of the rubber plug 6 .
还包括数据采集处理系统9,所述激光测距仪8与所述数据采集处理系统9通过电信号连接。A data collection and processing system 9 is also included, and the laser rangefinder 8 is connected to the data collection and processing system 9 through electrical signals.
一种表征高聚物溶胀特性的方法,包括如下步骤:A method for characterizing the swelling properties of polymers, comprising the steps of:
(1)计算需加入的高聚物的质量:(1) Calculate the mass of polymer to be added:
(A)量取用于溶解高聚物的溶剂,负压条件下静置除泡;(A) Measure the solvent used to dissolve the high polymer, and leave it to defoam under negative pressure;
所述负压条件为真空度≤-90KPa。The negative pressure condition is vacuum degree≤-90KPa.
(B)用激光测距仪8测量激光测距仪8到溶胀室2底部的距离,记为H0;(B) measure the distance from the laser range finder 8 to the bottom of the swelling chamber 2 with the laser range finder 8, denoted as H0;
当溶胀室2的尺寸、激光测距仪8的位置发生改变时,需重新采集H0值。When the size of the swelling chamber 2 and the position of the laser rangefinder 8 are changed, the H0 value needs to be collected again.
将步骤(1)中除泡完成的溶剂放入溶胀室2中,恒温一定时间;Put the solvent that has been defoamed in step (1) into the swelling chamber 2, and keep the temperature constant for a certain period of time;
所述恒温的操作步骤在恒温槽3中进行。The operation step of constant temperature is carried out in the constant temperature tank 3 .
所述恒温槽3的温度波动±0.05℃,数显分辩率为0.01℃,温度控制范围为0℃-90℃,容积优选为10L,加热介质优先为水。The temperature fluctuation of the constant temperature tank 3 is ±0.05°C, the digital display resolution is 0.01°C, the temperature control range is 0°C-90°C, the volume is preferably 10L, and the heating medium is preferably water.
(D)恒温完成后,激光测距仪8测量步骤(3)中溶剂的液面顶部距离激光测距仪8的距离,记为H1;(D) After the constant temperature is completed, the distance between the top of the liquid level of the solvent and the laser range finder 8 in the laser range finder 8 measurement step (3) is denoted as H 1 ;
(E)根据如下公式计算溶胀室2内溶剂的总体积V0:(E) Calculate the total volume V 0 of the solvent in the swelling chamber 2 according to the following formula:
V0=(H1-H0)×(Φ/2)2×3.14,其中Φ为溶胀室2的内径;V 0 =(H 1 -H 0 )×(Φ/2) 2 ×3.14, where Φ is the inner diameter of the swelling chamber 2;
(F)根据如下公式计算需加入溶胀室2内的高聚物的质量W0;(F) Calculate the mass W 0 of the high polymer that needs to be added to the swelling chamber 2 according to the following formula;
W0=V0/(1-α)×α,其中α为聚合物占溶胀后溶液的质量百分比;W 0 =V 0 /(1-α)×α, where α is the mass percentage of the polymer in the swollen solution;
(2)高聚物溶胀特性的表征:(2) Characterization of polymer swelling properties:
(A)称量质量为W1的高聚物,其中W1=W0±0.0005g,将称量好的高聚物放入溶胀室2中;(A) Weigh a high polymer with a mass of W 1 , wherein W 1 =W 0 ±0.0005g, and put the weighed high polymer into the swelling chamber 2;
高聚物在烘干后需在常温、湿度≤10%环境下称量,加入到溶胀室2前,不允许暴露在高湿环境下,避免因高聚物吸水影响高聚物在溶剂中高分子链的舒展、打开。After drying, the polymer needs to be weighed at room temperature and humidity ≤ 10%. Before adding to the swelling chamber 2, it is not allowed to be exposed to a high-humidity environment, so as to avoid the influence of the polymer on the solvent due to water absorption. The stretching and opening of the chain.
用钢网4将高聚物粉末压浸到溶剂中,将钢网4顶部的导杆5挂在胶塞6的开孔处,然后将胶塞6塞在溶胀室2的进液口;Use the steel mesh 4 to press-soak the polymer powder into the solvent, hang the guide rod 5 on the top of the steel mesh 4 at the opening of the rubber plug 6, and then plug the rubber plug 6 into the liquid inlet of the swelling chamber 2;
胶塞6开孔直径在满足操作要求的前提下,开孔直径越小越好,减少溶胀过程中由于NMP挥发引起的误差。On the premise that the hole diameter of the rubber plug 6 meets the operation requirements, the smaller the hole diameter, the better, so as to reduce the error caused by NMP volatilization during the swelling process.
以有机溶剂作为高聚物的溶剂时,例如使用NMP、环已烷溶解PVDF时,胶塞6主要耐腐蚀,胶塞6的材质优选材质三元乙丙;以纯水作为高聚物溶剂时,例如用纯水测量CMC溶胀特性时,普通橡胶材质的胶塞6即可。When an organic solvent is used as a polymer solvent, such as NMP or cyclohexane to dissolve PVDF, the rubber plug 6 is mainly corrosion-resistant, and the material of the rubber plug 6 is preferably EPDM; when pure water is used as a polymer solvent , for example, when measuring the swelling properties of CMC with pure water, the rubber plug 6 made of ordinary rubber is sufficient.
(C)激光测距仪8实时测量溶胀时间T及步骤(2)中(B)步骤中液面的顶部距离激光测距仪8的距离H2,并根据如下公式计算溶胀过程中溶液的体积:V2=(H2-H0)×(Φ/2)2×3.14;(C) laser rangefinder 8 real-time measurement swelling time T and the distance H2 of the top of the liquid surface in (B) step in step (2) from laser rangefinder 8, and calculate the volume of solution in the swelling process according to the following formula: V 2 =(H 2 -H 0 )×(Φ/2) 2 ×3.14;
(D)当溶胀表征值η不随溶胀时间T变化或变化很小时,停止测量,其中溶胀表征值η=V2/W1;绘制溶胀时间T和溶胀表征值η的关系曲线即为表征高聚物溶胀特性的曲线。(D) When the swelling characteristic value η does not change or changes very little with the swelling time T, stop the measurement, wherein the swelling characteristic value η=V 2 /W 1 ; draw the relationship curve between the swelling time T and the swelling characteristic value η to characterize the polymer The curve of the material swelling property.
所述H2、H1、H0、Φ的单位均为mm,所述V2、V1的单位均为mL,所述W1、W0的单位均为g,所述η的单位为mL/g。The units of H 2 , H 1 , H 0 and Φ are mm, the units of V 2 and V1 are mL, the units of W 1 and W 0 are g, and the unit of η is mL /g.
步骤(1)中(C)步骤的恒温温度优选为20-25℃。The constant temperature of step (C) in step (1) is preferably 20-25°C.
所述溶胀室2的内径值为5mm≤内径≤15mm,溶胀室2的精度不低于±0.01mm,溶胀室2的圆柱度不高于3um,溶胀室2的表面粗糙度不低于0.8,溶胀室2的高度值为100mm≤高度≤300mm。The inner diameter of the swelling chamber 2 is 5mm≤inner diameter≤15mm, the accuracy of the swelling chamber 2 is not less than ±0.01mm, the cylindricity of the swelling chamber 2 is not higher than 3um, and the surface roughness of the swelling chamber 2 is not lower than 0.8, The height value of the swelling chamber 2 is 100mm≤height≤300mm.
溶胀室2的内径越小、液面高度越高会使得测量更加准确,但是溶胀室2的内径不能太小,否则内径太小使得胶塞6较小,同样胶塞6上的开孔孔径会太小,导致激光测距仪8激光对准不够精确,影响测量数据的准确性,并且内径太小的话液面顶部可能会形成弯液面,造成测量不准确。The smaller the inner diameter of the swelling chamber 2 and the higher the liquid level will make the measurement more accurate, but the inner diameter of the swelling chamber 2 cannot be too small, otherwise the inner diameter is too small to make the rubber plug 6 smaller, and the opening aperture on the rubber plug 6 will also be smaller. If it is too small, the laser alignment of the laser range finder 8 is not accurate enough, which affects the accuracy of the measurement data. If the inner diameter is too small, a meniscus may be formed on the top of the liquid surface, resulting in inaccurate measurement.
溶胀过程中,随着高聚物在溶剂中不断溶胀,溶液的总体积会逐渐减小。During the swelling process, as the polymer continues to swell in the solvent, the total volume of the solution will gradually decrease.
溶胀室2是精密测量体积的工具,妥善保管、避免磕碰,清洗时使用高压水冲洗、压缩空气吹干,避免使用钢丝球等硬物造成划伤。The swelling chamber 2 is a tool for precise volume measurement. It should be kept properly and avoid bumping. When cleaning, it should be washed with high-pressure water and dried with compressed air to avoid scratches caused by hard objects such as steel wool.
所述导杆5的直径≤0.5mm,钢网4开有孔径≤20um的网孔。The diameter of the guide rod 5 is ≤0.5mm, and the steel mesh 4 is provided with a mesh with a diameter of ≤20um.
所述钢网4的材质优选为sus304。The material of the steel mesh 4 is preferably sus304.
使用天平称量高聚物的质量,天平精度为0.0001g。Use a balance to weigh the mass of the polymer with an accuracy of 0.0001 g.
将称量好的PVDF缓慢置入溶胀室2中,过程中注意避免粉末粘到溶胀室2的内壁上。Put the weighed PVDF into the swelling chamber 2 slowly, and pay attention to avoid the powder sticking to the inner wall of the swelling chamber 2 during the process.
激光测距仪8的测量精度为0.01mm,量程根据溶胀室2的高度选择,激光测距仪8优先的品牌为基恩士。The measurement accuracy of the laser rangefinder 8 is 0.01mm, and the range is selected according to the height of the swelling chamber 2. The preferred brand of the laser rangefinder 8 is KEYENCE.
数据采集处理系统9可自动读取激光测距仪8输出的数据并记录,数据采集时间、频率、间隔可通过系统窗口设置,采集频率≥1个/5s;并且具有形成时时监控曲线的功能,便于操作人员查看;具有原始数据导出功能。The data collection and processing system 9 can automatically read and record the data output by the laser range finder 8, the data collection time, frequency, and interval can be set through the system window, and the collection frequency is ≥1/5s; and it has the function of forming a monitoring curve from time to time, It is convenient for operators to check; it has the function of exporting original data.
溶剂的添加量需要略高于高分子聚合物溶胀溶解所需溶剂的量,减少因溶剂量过少影响高分子聚合物的溶胀速度。The amount of solvent added needs to be slightly higher than the amount of solvent required for the swelling and dissolving of the polymer, so as to reduce the influence of the swelling speed of the polymer due to too little amount of solvent.
实施例Example
准备工作:Preparation:
烧杯(200ml)一个,移液管(10ml)一个,洗耳球一个,真空腔连接真空泵;固定架调平;溶胀室内径10mm,高度200mm;PVDF样品两个,物性参数如下表1:One beaker (200ml), one pipette (10ml), one ear washing ball, the vacuum chamber is connected to the vacuum pump; the fixing frame is leveled; the diameter of the swelling chamber is 10mm, and the height is 200mm; two PVDF samples, the physical parameters are as follows in Table 1:
表1两个PVDF样品的参数列表Table 1 List of parameters of two PVDF samples
具体操作过程:Specific operation process:
样品A的测量:Measurement of sample A:
(1)高聚物NMP除泡:用烧杯取约100ml NMP,放置在负压腔体内除泡,真空度≤-90KPa,除泡时间30min;(1) Polymer NMP defoaming: take about 100ml NMP in a beaker, place it in a negative pressure chamber to defoam, the vacuum degree is ≤ -90KPa, and the defoaming time is 30min;
(2)NMP移取:用移液管取10ml NMP溶液到溶胀室2,打开恒温槽3,设定恒温20℃,恒温1小时。开启激光测距仪8,打开数据采集处理系统9,测量并计算得到溶胀室2内NMP的体积V0=10.0602ml;(2) NMP pipetting: Use a pipette to take 10ml of NMP solution into the swelling chamber 2, open the constant temperature tank 3, set the constant temperature to 20°C, and keep the temperature constant for 1 hour. Turn on the laser range finder 8, turn on the data acquisition and processing system 9, measure and calculate the volume V 0 of NMP in the swelling chamber 2 = 10.0602ml;
(3)PVDF称量:PVDF粉末在80℃下,真空度≤-90KPa下烘干12小时;依据V0=10.0602ml,根据下式计算溶胀得到质量百分比为6%的PVDF的质量:W0=V0/(1-6%)×6%=10.0602/(1-6%)×6%=0.6421g;(3) PVDF weighing: PVDF powder is dried for 12 hours at 80°C and vacuum degree ≤ -90KPa; according to V 0 =10.0602ml, the mass percentage of PVDF with a mass percentage of 6% is calculated according to the following formula: W 0 =V 0 /(1-6%)×6%=10.0602/(1-6%)×6%=0.6421g;
称取W1=0.6425g,将W1实际值粉输入到数据采集处理系统9中。Weigh W 1 =0.6425g, and input the actual value of W 1 into the data acquisition and processing system 9 .
(4)将称量好的PVDF粉末缓慢送入溶胀室2内,用钢网4将浮在液面上的粉末缓慢压浸到液面下,目视粉末压浸到NMP溶剂液面中间位置较佳,胶塞6压盖在溶胀室2的进液口;(4) Slowly send the weighed PVDF powder into the swelling chamber 2, use steel mesh 4 to slowly press-immerse the powder floating on the liquid surface under the liquid surface, and visually inspect the powder to press-immerse in the middle of the NMP solvent liquid surface Preferably, the rubber plug 6 is pressed against the liquid inlet of the swelling chamber 2;
(5)数据采集处理系统9测量并计算得到V1,并将V1转化成溶胀表征值η;(5) The data acquisition and processing system 9 measures and calculates V 1 , and converts V 1 into a swelling characteristic value η;
(6)在数据采集处理系统9上设置执行模式:(6) execution mode is set on the data acquisition and processing system 9:
第一步:数据采集间隔10s,执行时间12小时;The first step: the data collection interval is 10s, and the execution time is 12 hours;
第二步:数据采集间隔60s,执行时间12小时;The second step: the data collection interval is 60s, and the execution time is 12 hours;
第三步:数据采集间隔120s,执行时间24小时,结束;The third step: the data collection interval is 120s, the execution time is 24 hours, and the end;
样品B的测量:Measurement of sample B:
(7)重复以上步骤(1)至步骤(6),测试样品B;(7) Repeat above step (1) to step (6), test sample B;
(8)导出数据,整理;(8) Export data and organize;
(9)数据分析:(9) Data analysis:
以上两样品是同一厂家不同型号两产品,从特征曲线对比可得出:The above two samples are two products of different models from the same manufacturer. From the comparison of the characteristic curves, it can be concluded that:
样品A达到两元匀相时间约30小时,样品B需要46小时左右,因此样品A溶胀特性优于样品B;It takes about 30 hours for sample A to reach binary homogeneous phase, and about 46 hours for sample B, so the swelling property of sample A is better than that of sample B;
溶胀初期,NMP溶剂进入样品A粉体颗粒的能力优于样品B;In the early stage of swelling, the ability of NMP solvent to enter the powder particles of sample A is better than that of sample B;
溶胀后期,样品B的高分子舒展、打开不如样品A;In the later stage of swelling, the stretching and opening of the polymer of sample B is not as good as that of sample A;
假定样品A是当前使用的产品,根据样品A的制胶生产参数,可以推测样品B在搅拌时间、温度、转速等方面需在样品A的基础上稍作提高才能达到品质优良的胶液。Assuming that sample A is the currently used product, according to the glue production parameters of sample A, it can be speculated that sample B needs to improve the stirring time, temperature, rotation speed, etc. of sample A slightly on the basis of sample A to achieve high-quality glue.
以上所述仅为本发明创造的较佳实施例而已,并不用以限制本发明创造,凡在本发明创造的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明创造的保护范围之内。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 Within the scope of protection of the present invention.
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