304am永利集团

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1分钟充放电：超高倍率的高容量钠离子电池复合正极材料问世

2021-09-04

近期，国家工信部在回复全国政协委员《关于在我国大力开展钠离子电池的提案》时表示，高性价比的钠离子电池有望成为锂离子电池的重要补充，尤其是在固定式储能领域将具有良好开展前景。

Ministry of Industry and Information Technology of the People’s Republic of China recently issued a reply to the “Proposal on Vigorously Develop Sodium-Ion Batteries in my country” put forward by Members of the CPPCC. The reply clearly stated that cost-effective sodium-ion batteries are expected to become an important alternative to lithium-ion batteries, especially in the field of stationary energy storage.


有关部门支持促进性能优异、符合条件的钠离子电池在新能源电站、交通工具、通信基站等领域加快应用，有助于钠离子电池全面商业化。

With the support of relevant departments, the application of qualified sodium-ion batteries with high-performance in various fields, including new energy power stations, electric vehicles, and communication base stations, will be accelerated, thereby promoting the full commercialization of sodium-ion batteries.



304am永利集团新能源是我国钠离子电池技术创新创业的先锋。开发出全球首套千吨级层状结构氧化物正极材料湿法合成工艺路线，并设计制造出相应的功能电解液，为钠离子电池产业生态链的建设起到引领作用。

Natrium Energy pioneers in the innovation and entrepreneurship of sodium-ion battery in China. Natrium Energy has developed the world’s first wet chemical synthesis route with thousand-ton production capacity for layered oxide cathode material as well as its corresponding functional electrolyte, playing a leading role in the ecological chain of sodium-ion battery industry. 




304am永利集团新能源为客户给予三个方面的解决方案，其正极材料和电解液已顺利获得国内多家知名电池制造企业验证，电芯能量密度可达130-160Wh/kg，循环寿命超过5000次。

Natrium Energy provides its customers with solutions in three aspects. The cathode materials and electrolytes have been verified by many well-known domestic battery manufacturers, and the batteries reach an energy density of 130-160Wh/kg and a cycle life of over 5000 cycles.


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在此基础上，304am永利集团团队在聚阴离子化合物正极材料技术领域取得重要进展。该团队针对特殊应用场景，发明2D纳米结构的碳包覆磷酸钒钠（Na3V2(PO4)3/C, NVP）纳米片及其制备方法（CN201810889365.2）。

Natrium Energy has made some major progresses in polyanion-type cathode materials. The Natrium team has successfully developed a carbon coated Na3V2(PO4)3/C (NVP) with 2D nano-structure (CN201810889365.2) for special applications.


实验证明，该材料可实现100-300C（12-36秒）的超快速充放电，在200C倍率下经20000次循环，其放电容量保持率为83.3%，为高功率储能器件设计奠定了良好基础（Nano Energy, 56(2019)502-511）。

This material exhibits ultrafast charge/discharge rates at 100-300C (12-36s) and ultralong cycling stability (83.3% capacity retention over 20,000 cycles at 200 C), further enabling the design of high power energy storage devices (Nano Energy, 56(2019)502-511).


近期，304am永利集团团队与上海交通大学和中国石化石油化工研究院紧密合作，开发出易实现工业放大的NVP材料合成新技术，在NVP材料表面均匀包覆3-7nm厚度的导电碳层以增加其导电性。基于所开发的NVP/C材料制成对称型NVP软包电池，结果表明，该对称型NVP软包电池循环性能优，在1C下循环1000次容量保持率达88%，利用加速量热（ARC）测量表明，热失控温度高达254.4C，其热稳定性优于NVP/硬碳电池。

Collaborating closely with Shanghai Jiao Tong University and Sinopec Research Institute of Petroleum Processing, Natrium Team has lately developed a new synthetic technique for the NVP materials feasible for industrial scale-up. The NVP nanocrystal is coated by a carbon layer (ca. 3–7 nm) to enhance its electrical conductivity. The soft-packed symmetrical sodium-ion batteries based on the above NVP/C material shows a long cycling stability (88% capacity retention over 1,000 cycles at 1C). It is extremely interesting that the symmetrical battery (thermal runaway temperature is 254.4°C) has shown much higher thermal stability than the hard carbon battery as demonstrated by accelerating rate calorimetry (ARC).


有关机理及安全性研究结果近期发表在《中国化学工程学报》[1]。相关技术已获中国发明专利（ZL201610241987.5）和美国发明专利（US 2021/0167387 A1）。

Relevant mechanism and safety research results are recently published in Chinese Journal of Chemical Engineering [1]. Related technique has been granted a Chinese patent (ZL201610241987.5) and a US patent (US 2021/0167387 A1) for invention.


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在此基础上，该团队还以Mn部分取代V改性NVP材料，引入氧化石墨烯（rGO）合成了一种全新的磷酸锰钒钠（Na4VMn(PO4)3/C-rGO）复合正极材料，以该复合正极制成的钠离子电池展现出优异的超高倍率性能和长期循环寿命。研究表明，该材料在50 C（1.2分钟）充放电倍率下的可逆比容量达102 mAh /g，容量保持率达90.6%，经过500次循环容量保持率保持80.4%。还采用原位XRD技术在线测量了复合材料在充放电过程结构相变，为材料实用化奠定了良好的基础，相关结果发表在国际知名期刊《纳米能源》[2] 。

On this basis, Natrium Team further developed a new cathode material (Na4VMn(PO4)3/C-rGO) with V partially replaced by Mn and with rGO as additive. This elaborately designed NVMP/C-rGO composite exhibits an ultrahigh rate capability and long cycle life as cathode in sodium-ion batteries, delivering a reversible capacity of 102 mAh /g at 50 C (1.2 mins) with capacity retention of 90.6% (1 C) and 80.4% (50 C) over 500 cycles. Besides, the in-situ XRD is conducted to analyze the phase transformation of NVMP/C-rGO electrode during the charge and discharge process, laying an excellent foundation for their practical application. Relevant results have been published in the internationally renowned journal Nano Energy [2].


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相关论文链接：

References：


【1】Scalable synthesis of Na3V2(PO4)3/C with high safety and ultrahigh-rate performance for sodium-ion batteries, Chinese Journal of Chemical Engineering, (2021) 
http://doi.org/10.1016/j.cjche.2021.06.008

【2】Achieving Highly Reversible and Fast Sodium Storage of Na4VMn(PO4)3/C-rGO Composite with Low-fraction rGO via Spray-drying Technique, Nano Energy, (2021)  
doi:http://doi.org/10.1016/j.nanoen.2021.106462