【编辑推荐】2024年2期综述、环境保护、产学研

王江林，周丽，代少振，刘孝伟，黄思淼^*

（ 超威电源集团有限公司，浙江 湖州 313100 ）

摘要：锌-二氧化锰电池的开路电压约为1.55 V，可分为一次碱锰电池和二次锌锰电池。在用于可充电锌锰电池中，MnO₂及其复合物由于成本低（Zn/MnO₂碱性电池的成本为10~65美元/kW·h）、比能量高（理论比能量为308 W·h/kg）、自身安全性好、电化学性能好、无毒环保，并且具有多晶型、结构可控、高孔隙率等特性，被广泛应用在锌锰干电池、锂离子电池以及超级电容器中，吸引了越来越多的关注。但是，在碱性体系中，MnO₂在高浓度的KOH溶液下充放电形成稳定结构尖晶石结构的Mn₃O₄，导致电池容量极具衰减，降低了电池的稳定性低，只能实现50次的充电的循环，大大限制了其应用范围。近年来，含锌离子、锰离子的中性电解液的使用，实现了锌离子在二氧化锰中嵌入-脱出的反应，大大提高了锌锰电池的循环性能。但是Zn/MnO₂电池仍存在嵌入-脱出和溶解-沉积的内在机制，且电池的高功率放电性能低，电池机理更加复杂。分别对二氧化锰在碱性电解液和中性电解液体系下，对锰正极添加剂、纳米材料的开发、新型电解液、高导电碳基复合材料应用等方面开展总结和讨论，以优化放电机制也可提升电池的容量、延长循环寿命。探讨了抑制不可逆相的生成和促进反应向生成可逆相的途径，有望提出合理的思路，以取得突破性进展。为设计和制造高性能可充电锌基电池提供指导。

Research progress and prospects of manganese cathode in secondary zinc-manganese battery

WANG Jianglin，ZHOU Li，DAI Shaozhen，LIU Xiaowei，HUANG Simiao^*

( Chilwee Power Co., Ltd., Huzhou, Zhejiang 313100, China )

Abstract: The zinc-manganese dioxide battery has an open circuit voltage of about 1.55 V and can be divided into primary alkaline manganese batteries and secondary zinc-manganese batteries. In the use of rechargeable Zn-manganese batteries, MnO₂ and its compounds due to low cost (Zn/MnO₂ alkaline battery cost of 10~65 US dollars /kW·h), high specific energy (theoretical specific energy of 308 W·h/kg), good safety, electrochemical performance, non-toxic environmental protection. Moreover, it has the characteristics of polycrystalline, controllable structure, and high porosity, which are widely used in zinc-manganese dry batteries, Li-ion batteries, and supercapacitors, attracting more and more attention. However, in the alkaline system, MnO₂ charges and discharges in a high concentration of KOH solution to form a stable structure of spinel structure Mn₃O₄, resulting in a very attenuating battery capacity, reducing the low stability of the battery, and can only achieve 50 charging cycles, which greatly limits its application range. In recent years, the use of neutral electrolytes containing zinc ion and manganese ion has realized the reaction of zinc ion intercalation-deintercalation in manganese dioxide, which greatly improves the cycle performance of zinc-manganese batteries. However, Zn/MnO₂ batteries still have internal mechanisms of intercalation-deintercalation and dissolution-deposition, and the high power discharge performance of the batteries is low, and the battery mechanism is more complex. The development of manganese dioxide anode additives, nanomaterials, new electrolytes, and applications of highly conductive carbon-based composites in alkaline electrolyte and neutral electrolyte systems are summarized and discussed, respectively, in order to optimize the discharge mechanism and increase the capacity of batteries and extend the cycle life. The ways of inhibiting the formation of irreversible phase and promoting the reaction to the formation of reversible phase are discussed. Guidance for the design and manufacture of high-performance rechargeable zinc-based batteries is provided.

田浩然，夏兰^*

（ 宁波大学海运学院，浙江 宁波 315832 ）

摘要：锂离子电池已广泛应用于中小型储能设备，而热失控是导致电池发生安全问题的主要原因。电解液是热失控链条中的重要一环，降低其可燃性有助于保障电池安全。针对目前商业电解液闪点低、易燃等问题，已有很多解决方案。本文总结了几种锂离子电池耐燃电解液体系，包括含磷、含氟和含硅有机阻燃剂等不燃体系，含磷阻燃剂的阻燃效率及电池兼容性等综合性能较好，含氟代溶剂闪点高但阻燃效率一般，而硅基阻燃剂热稳定性好但很难作为纯溶剂使用。最后，对锂离子电池耐燃电解液的发展前景进行展望。

Research progress in flame-retardant electrolytes for Li-ion battery

TIAN Haoran，XIA Lan^*

(Faculty of Maritime and Transportation, Ningbo University, Ningbo, Zhejiang 315832, China)

Abstract: Li-ion batteries have been widely applied in mini-sized and medium-sized energy storage devices. Thermal runaway is the main cause of battery safety problems. As a vital link of the thermal runaway chain, decreasing the flammability of electrolytes is beneficial to the safety of Li-ion batteries. At present, there has been a series of strategies to lower the ignition of commercial electrolytes. The flame-retardant (FR) and non-flammable electrolyte systems, including phosphorus-containing, fluorine-containing, and silicon-containing organic compounds-based FR electrolytes are summarized. Considering their high FR efficiency and their miscibility with EC-based electrolytes, phosphorus-based compounds, are the most common FRs used in LIBs; fluorinated solvents have high flash points but low FR efficiency; silicone-based FR has good thermal stability, but are difficult to use as pure solvents. In the end, the future developments of FR electrolytes for Li-ion batteries are prospected.

钟恺为¹，王长宏^1∗，吕琪铭²，张志会¹，丘榕芳¹

(1. 广东工业大学材料与能源学院，广东 广州 510006；
2. 广州城投综合能源投资经营管理有限公司，广东 广州 510006)

摘要：为实现双碳目标，新能源汽车和新型电力系统迅速发展，锂离子电池的能量密度不断提升，但锂离子电池的热管理与热安全问题成为了制约新能源汽车及新型电力系统的重大瓶颈。浸没式冷却是未来极具突破该瓶颈潜力的热管理技术之一。展示了浸没式冷却与传统冷却技术在载热能力、接触面积、接触热阻和抑制热失控等方面的对比，讲述了浸没式冷却的工作机理，归纳并比较了矿物油、硅油、氟化液等5种目前常用的冷却工质及物性参数，讲述了冷却工质改性的作用，并罗列了热导率等改性关键参数的相关研究，介绍了单相浸没式冷却、两相浸没式冷却的研究进展，梳理了通过调整流道结构与传热附件对质量、泵功、流量分配和冷却性能等方面进行优化的研究。对浸没式冷却在热失控的抑制机理进行初步探讨，将浸没式冷却技术的研究总结为冷却工质改性、冷却性能强化、抑制热失控机理研究。

Research progress in immersion cooling for Li-ion battery

ZHONG Kaiwei¹, WANG Changhong^1∗, LYU Qiming², ZHANG Zhihui¹, QIU Rongfang ¹

(1. School of Materials and Energy, Guangdong University of Technology, Guangzhou, Guangdong 510006, China; 2. Guangzhou City Construction Investment Group, Guangzhou, Guangdong 510006, China)

Abstract: To achieve the carbon peaking and carbon neutrality goals, new energy vehicles and new power systems develop rapidly, and the energy density of Li-ion batteries grows constantly. However, thermal management and safety issues of Li-ion batteries have become significant bottlenecks constraining the advancement of new energy vehicles and new power systems. Immersion cooling emerges as one of the most promising thermal management technologies to overcome these bottlenecks in the future. The advantages of immersion cooling compared with traditional cooling technology in heat carrying capacity, contact area, contact thermal resistance, and suppression of thermal runaway are listed. The mechanism of immersion cooling is described. The five commonly used working fluids, including mineral oil, silicone oil, and fluorinated liquids, are summarized, along with a comparison of their physical properties. The purpose of modifications to the working medium is described, and the relevant research on key parameters of modification such as thermal conductivity is listed. The research progress of single-phase immersion cooling and two-phase immersion cooling technology is introduced, and the research on modifying the flow channel structure and heat transfer accessory to optimize quality, pump power, flow distribution, and heat transfer performance is summarized. The mechanism of restraining thermal runaway by immersion cooling is preliminarily discussed. The research of immersion cooling technology is summarized as the modification of working fluids, the adjustment of structural parameters to strengthen the heat transfer performance of the system, and the study of the mechanism of immersion cooling to inhibit thermal runaway.

李海鹏^∗，孙邦兴，李嘉烨

(中国船舶集团有限公司第七一八研究所，河北 邯郸 056027)

摘要：发展高能效、低成本、零排放的可再生能源电解制氢技术是实现“碳中和”“碳达峰”的关键。然而，目前传统的化石制氢技术仍然是全球氢气的主要来源，不仅耗能高且产生大量的二氧化碳，不符合可持续发展需求。相较之下，随着可再生能源价格持续下降，利用可再生能源电解水制氢有望成为未来氢能的主流技术路线。基于此，本文围绕当前主流的绿色制氢技术的最新研究进展，重点阐述了电解水制氢（碱性电解水制氢、阴离子交换膜电解水制氢、质子交换膜电解水制氢、固体氧化物电解水制氢等）、太阳能分解水制氢（光催化法、光热分解法和光电化学法等）以及生物质制氢等“绿氢”技术的产氢机理、技术难题和应用前景。同时，还分析和讨论了未来绿色制氢技术的应用前景和发展方向。

Progress of green hydrogen production technology under dual carbon goal

LI Haipeng^∗, SUN Bangxing, LI Jiaye

(718th Research Institute of China State Shipbuilding Corporation Limited, Handan, Hebei 056027, China)

Abstract: The development of energy-efficient, low-cost, zero-emission renewable energy technologies for electrolytic hydrogen production represents a pivotal step towards achieving "carbon neutrality" and "carbon peaking". However, traditional fossil-based hydrogen production continues to represent the dominant source of hydrogen globally, a process that is not only energy-intensive but also results in the generation of a considerable quantity of carbon dioxide, a byproduct that is not aligned with the principles of sustainable development. Conversely, as the cost of renewable energy continues to decline, hydrogen production from electrolyzed water using renewable energy is anticipated to become the dominant technology pathway for hydrogen energy in the future. This paper will focus on the latest research progress of current mainstream green hydrogen production technologies, with a particular emphasis on the hydrogen production mechanisms of electrolysis water (alkaline electrolysis water, anion-exchange membrane electrolysis water, proton-exchange membrane electrolysis water, and solid oxide electrolysis water), solar energy decomposition of water for hydrogen production (photocatalytic, photothermal decomposition, and photoelectrochemical), and biomass hydrogen production. It will also consider other "green hydrogen" technologies. This paper also examines the hydrogen production mechanisms, technical difficulties, and application prospects of "green hydrogen" technologies, including solar decomposition of water to produce hydrogen (photocatalysis, photothermal decomposition, and photoelectrochemistry) and biomass to produce hydrogen. Furthermore, the application prospects and development direction of future green hydrogen production technologies are also analyzed and discussed.

毕海军^1∗，夏冬松²，秦宽²，曹成茂³

(1. 安徽农业大学茶与食品科技学院，安徽 合肥 230036；2. 安徽农业大学工学院，安徽 合肥 230036；3. 安徽智能农机装备工程实验室，安徽 合肥 230036)

摘要:废旧锂离子电池的涡流分选工艺由于影响参数过多，分选效果并不理想。为探明各参数对分选效果的影响，提高涡流分选法的分离效率，开展废旧磷酸铁锂锂离子电池破碎产物的涡流分选研究。利用COMSOL仿真软件模拟磁辊交变磁场分布，建立产物在交变磁场的受力模型与运动模型，研究磁辊长度、磁极对数、磁辊半径、进料速度、磁辊转速、颗粒尺寸和颗粒形状等因素对分选效果的影响，提出将传送带摩擦因数纳入影响参数之中进行模拟，以指导涡流分选模型的建立。上述因素均会影响颗粒的运动轨迹，减小摩擦因数有利于提高分选效率，颗粒尺寸和形状是主要的影响因素。

Model and influencing factors of eddy current separating of spent Li-ion battery

BI Haijun^1∗, XIA Dongsong², QIN Kuan², CAO Chengmao³

(1. School of Tea and Food Science & Technology, Anhui Agricultural University, Hefei, Anhui 230036, China; 2. School of Engineering, Anhui Agricultural University, Hefei, Anhui 230036, China; 3. Anhui Intelligent Agricultural Machinery Equipment Engineering Laboratory, Hefei, Anhui 230036, China)

Abstract: In the eddy current separating process of spent Li-ion battery, the separating effect is not satisfactory due to the multitude of influencing parameters. To understand the impact of various parameters on the separating effect and improve the separation efficiency of the eddy current separating method, a study is conducted on the eddy current separating of crushed products from spent lithium iron phosphate Li-ion batteries. Using COMSOL simulation software, the alternating magnetic field distribution of the magnetic roller is simulated. A force model and motion model for the products in the alternating magnetic field are established. Factors such as magnetic roller length, number of magnetic poles, magnetic roller radius, feed speed, magnetic roller rotational speed, particle size, and particle shape are studied for their influence on the separating effect. Friction factors on the conveyor belt are included in the simulated parameters to guide the establishment of the eddy current separating model. The above factors will affect the particles′ trajectory, reducing friction factors is beneficial to improve separating efficiency. Particle size and shape are the primary influencing factors.

王亚丽¹，金占双^1∗，马昌²

(1. 河北北方学院理学院，河北 张家口 075000；2. 天津工业大学材料科学与工程学院，天津 300387)

摘要：新工科专业侧重于培养具有创新能力、跨学科素养、实践操作能力和国际视野的复合型人才。以新能源电池专业为研究对象，分析新工科对新能源电池专业人才的要求和定位，以及目前专业的课程设计教学方面存在的问题，提出制定符合新工科建设要求的课程教学培养方案、注重新工科特色和学科的深度交叉融合等教学改革方面的具体措施。 

Teaching reform of new energy battery specialized courses under the background of new engineering

WANG Yali¹, JIN Zhanshuang^1∗, MA Chang²

(1. College of Science, Hebei North University, Zhangjiakou, Hebei 075000, China; 2. School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China)

Abstract: The new engineering major focuses on cultivating compound talents with innovative ability, interdisciplinary accomplishment, practical operation ability and international vision. Taking the major of new energy battery as the research object, the requirements and positioning of new engineering professionals for new energy battery are analyzed, as well as the existing problems in the course design and teaching. The specific measures for teaching reform such as formulating curriculum teaching and training programs that meet the requirements of new engineering construction, focusing on the characteristics of new engineering and the deep cross-integration of disciplines are put forward.

徐曼^1∗，徐自为²

(1. 商丘职业技术学院质量管理与发展规划处，河南 商丘 476000；2. 北京师范大学地理科学学部，北京 100875)

摘要：燃料电池专业课程具有知识点多、理论与实践并重等特点,对学生的要求较高。目前，燃料电池专业教学存在师生互动少、教学体系不够完善、教学资料缺乏系统性等问题。“互联网+教育”可灵活应用现代化信息技术解决燃料电池专业课程教学中的问题，提升教学质量，为院校培养出高质量复合型专业人才。基于“互联网+教育”模式对燃料电池专业课程提出建设策略，包括课程内容设计、虚拟仿真平台建设、指导答疑系统开发以及线上-线下实践平台的搭建等。

Curriculum construction of fuel cell specialty from the perspective of "Internet+education"

XU Man^1∗, XU Ziwei²

(1. Quality Management and Development Planning Department, Shangqiu Polytechnic, Shangqiu, Henan 476000, China; 2. Faculty of Geographical Science, Beijing Normal University, Beijing 100875, China)

Abstract: The fuel cell professional course has the characteristics of many knowledge points, theories, and practices, has high requirements for students. At present, there are problems in the teaching of fuel cell majors, such as less interaction between teachers and students, less perfect teaching systems and less systematic teaching materials. The " Internet + education" can flexibly apply modern information technology to solve problems in the teaching of fuel cell professional courses, improve the teaching quality, cultivate high-quality compound professionals for colleges and universities. Based on the " Internet + education " mode, the construction strategy of fuel cell professional course is proposed, including course content design, virtual simulation platform construction, guide answering system development and online-offline practice platform construction.

Teaching reform of new energy battery specialized courses under the background of new engineering

WANG Yali¹, JIN Zhanshuang^1∗, MA Chang²

(1. College of Science, Hebei North University, Zhangjiakou, Hebei 075000, China; 2. School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China)

Abstract: The new engineering major focuses on cultivating compound talents with innovative ability, interdisciplinary accomplishment, practical operation ability and international vision. Taking the major of new energy battery as the research object, the requirements and positioning of new engineering professionals for new energy battery are analyzed, as well as the existing problems in the course design and teaching. The specific measures for teaching reform such as formulating curriculum teaching and training programs that meet the requirements of new engineering construction, focusing on the characteristics of new engineering and the deep cross-integration of disciplines are put forward.

徐树正^1∗，石璐²

(1. 郑州商学院文学与新闻传播学院，河南 郑州 451200；2. 首都师范大学教育学院，北京 100048)

摘要：燃料电池技术发展迅速，传统的教学模式存在产学脱节、场景单一化等问题，已无法满足行业的需求。为提升学生学习燃料电池课程的效果，基于产教融合，提出对燃料电池课程进行专业教学体系建设，改进教学模式，建设实践教学平台，设计专业课程内容，并初步评估教学实践成效。

Construction of fuel cell professional teaching under the background of integration of industry and education

XU Shuzheng^1∗, SHI Lu²

(1. College of Literature and Journalism, Zhengzhou Business University, Zhengzhou, Henan 451200, China; 2. College of Education, Capital Normal University, Beijing 100048, China)

Abstract: With the rapid development of fuel cell technology, traditional teaching models have problems such as industry academia disconnection and single scenarios, which can no longer meet the needs of the industry. To enhance the effectiveness of students learning fuel cell courses, based on the integration of production and education, it is proposed to construct a professional teaching system for fuel cell courses, improve the teaching mode, build a practical teaching platform, design professional course content, preliminarily evaluate the effectiveness of teaching practice.