Review of Research on Cobalt Free Double-Element Doped Spinel Type Lithium Manganate AITranslate

［1］任健，马梓尚，王媛铎，欧骥若，陈泰强，郑时有. 富镍层状正极微裂纹产生机制及其应对策略 ［J］. 稀有金属，2022，46（6）： 736.

J Ren，Z S Ma，Y D Wang，J R Ou，T Q Chen，S Y Zheng. Generation mechanism of microcracks in nickel-rich layered anode and its response strategy ［J］. Chinese Journal of Rare Metals，2022，46（6）： 736.

［2］Margarette S J，Bangeppagari M，Vijaya B K，Madhuri S J，Veeraiah V，Sangaraju S，Ayyar M，Ravi M. Ce and Cu co-doped LiMn2O4 cathode material： synthesis，characterization and electrochemical performances ［J］. Ceramics International，2024，50（3）： 4955.

［3］Benedek R. Role of disproportionation in the dissolution of mn from lithium manganate spinel ［J］. The Journal of Physical Chemistry C，2017，121（40）： 22049.

［4］欧镇滔，罗刚，冯小勇，郭子依，李建伟，秦伟. 碳包覆硒化锌用作高性能锂离子电池负极材料 ［J］. 铜业工程，2024，（1）： 81.

Z T Ou，G Luo，X Y Feng，J W Li，W Qin. Carbon-coated ZnSe nanoparticles for high-performance lithium-ions battery anode ［J］. Copper Engineering，2024，（1）： 81.

［5］Wang J，Xu Y，Niu Y，Liu Y，Yao X. Lithium-ion conductivity epitaxial layer contributing to the structure and cycling stability of LiMn2O4 cathodes ［J］. ACS Sustainable Chemistry & Engineering，2023，11（14）： 5408.

［6］董恩华，纪鸿文，刘秉国，宇文超. 微波法一步合成LiNi1/3Co1/3Mn1/3O2材料及其性能研究 ［J］. 有色金属工程，2022，12（6）： 14.

E H Dong，H W Ji，B G Liu，W C Yu. One step synthesis of LiNi1/3Co1/3Mn1/3O2 by microwave method and its properties ［J］. Nonferrous Metals Engineering，2022，12（6）： 14.

［7］Yang S，Yan P，Bao W，Zhu H，Cai X，Zhao L，Zhang Y，Lin W，Deng Y，Wu Y，Xie J. Surface magnesium substitution at spinel lithium manganate 8a tetrahedral sites for suppressed manganese dissolution and enhanced cycle stability ［J］. ACS Energy Letters，2023，8（10）： 4278.

［8］Hunter J C. Preparation of a new crystal form of manganese dioxide： λ-MnO2 ［J］. Journal of Solid State Chemistry，1981，39（2）： 142.

［9］Ma Y Y，lv L，Dai Y W，Zhou Q H，Cheng J M，Li H L，Hu W. A First-principles study on the structure and electronic structure of Ti-doped spinel LiMn2O4 for Li-ion batteries ［J］. Journal of Electronic Materials，2021，51（1）： 77.

［10］Yang M，Liang Q M，Guo Y J，Guo J M，Xiang M W，Bai W，Liu X F. Boosting high-rate capacity and long-cycle stability of spinel LiMn2O4 by the Cr Al co-doping strategy ［J］. Journal of Energy Storage，2023，72： 108528.

［11］Zhang B，Zhang Y J，Zhang Q，Gao Y F，Zhu B W，Gong R，Wang Z W，Bu J J，Lian Z，Zhou K，Dong P，Zhang Y N. Spinel LiMn2O4 with remarkable electrochemical performances by synergistic enhancement of double-cation （Sm3+，Mo6+） doping for Li-ion batteries ［J］. JOM，2022，74（12）： 4672.

［12］Liang Q M，Wang Z L，Bai W，Guo J M，Xiang M W，Liu X F，Bai H L. Stimulative formation of truncated octahedral LiMn2O4 by Cr and Al co-doping for use in durable cycling Li-ion batteries ［J］. Dalton Transactions，2021，50（46）： 17052.

［13］Yang Z R，Wang Y J，Chen X C，Wu H，Zhang Y. Mg2+ and Ti4+ co-doped spinel LiMn2O4 as lithium‐ion battery cathode ［J］. Chemistry Select，2019，4（33）： 9583.

［14］Nageswara B，Narsimulu D，Srinadhu E S，Satyanarayana N. Structural，electrical，and dielectric properties of nickel-doped spinel LiMn2O4 nanorods ［J］. Ionics，2018，25（3）： 981.

［15］Pugazhendhi A，Ellappan S，Kumaresan I，Paramasivam M. Dielectric and conduction mechanism studies of Ni doped LiMn2O4 synthesized by solution combustion method ［J］. Ionics，2018，24（12）： 3745.

［16］Liu W H，Xu H H，Zhou Q H，Dai Y W，Hu W，Li H L. The performance of Ni-doped spinel-type LiMn2O4 for Li-ion batteries： first-principles calculation ［J］. Journal of Electronic Materials，2020，49（9）： 5523.

［17］Jiang J B，Liang L W，Li D，Xiao J，Peng Z D，Du K，Cao Y B，Hu G R，Jiang F. Synthesis of high-performance cycling LiNixMn2−xO4 （x≤0.10） as cathode material for lithium batteries ［J］. Journal of Nanoscience and Nanotechnology，2017，17（12）： 9182.

［18］Zhu J Y，Liu Q，Xiang M W，Guo J M，Bai H L，Liu X F，Su C W，Bai W. Facile synthesis of truncated octahedron LiNi0.10Mn1.90O4 for high-performance Li-ion batteries ［J］. Ceramics International，2020，46（10）： 14516.

［19］Xu W Q，Li Q L，Sui F R，Guo S M，Qi R J，Yan C Q，Chen L J，Xia S B，Guo J M，Li Z，Huang R，Cheng F X. Unveiling the role of Ni doping in the electrochemical performance improvement of the LiMn2O4 cathodes ［J］. Applied Surface Science，2023，624： 157142.

［20］Chen M，Chen P，Yang F，Song H，Liao S. Ni，Mo co-doped lithium manganate with significantly enhanced discharge capacity and cycling stability ［J］. Electrochimica Acta，2016，206： 356.

［21］Iqbal A，Khan A M，Wang T，Li D，Gao Y. Effect of Ni and Cu substitution on the crystal structure，morphology and electrochemical performance of spinel LiMn2O4 ［J］. International Journal of Electrochemical Science，2019，14（1）： 929.

［22］Su C W，Chen R F，Sa Z Y，Li H，Xiang M W，Guo J M，Bai W，Liu X F. High-capacity and superior behavior of the Ni-Cu co-doped spinel LiMn2O4 cathodes rapidly prepared via microwave-induced solution flameless combustion ［J］. New Journal of Chemistry，2021，45（35）： 16101.

［23］Wang S M，Xiang M W，Lu Y，Guo J M，Su C W，Bai H L，Liu X F. Facile solid-state combustion synthesis of Al-Ni dual-doped LiMn2O4 cathode materials ［J］. Journal of Materials Science： Materials in Electronics，2020，31（8）： 6036.

［24］Ji Y，Liu H L，Guo Y J，Guo J M，Xiang M W，Bai W，Liu X F，Bai H L. Improved capacity retention and ultralong cycle performance of Ni-Fe co-doped LiMn2O4 cathode material at high current densities ［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects，2022，648： 129259.

［25］Luo Y X，Liu Q，Guo Y J，Guo J M，Xiang M W，Bai W，Liu X F，Bai H L. Improved long cycle performance of LiMn2O4 cathode material by Ni-B co-doping combined with truncated octahedron morphology ［J］. Journal of Alloys and Compounds，2022，924： 166537.

［26］Liang L Q，Liu H Y，Liang Y S，Li Y Y，Bai W，Guo J M，Xiang M W. Preparation of Ni-Zn dual-doped polyhedral LiMn2O4 for endurable cycling lithium ion batteries at high rate ［J］. Vacuum，2023，213： 112109.

［27］Yu Y，Xiang M W，Guo J M，Su C W，Liu X F，Bai H L，Bai W，Duan K J. Enhancing high-rate and elevated-temperature properties of Ni-Mg co-doped LiMn2O4 cathodes for Li-ion batteries ［J］. Journal of Colloid and Interface Science，2019，555： 64.

［28］Yu Y，Guo J M，Xiang M W，Su C W，Liu X F，Bai H L，Bai W，Duan K J. Enhancing the durable performance of LiMn2O4 at high-rate and elevated temperature by nickel-magnesium dual doping ［J］. Scientific Reports，2019，9（1）： 16864.

［29］Wang J，Nie P，Xu G Y，Jiang J M，Wu Y T，Fu R R，Dou H，Zhang X G. High‐voltage LiNi0.45Cr0.1Mn1.45O4 cathode with superlong cycle performance for wide temperature lithium-ion batteries ［J］. Advanced Functional Materials，2018，28（4）： 1704808.1.

［30］Mao J，Dai K H，Xuan M J，Shao G S，Qiao R M，Yang W L，Battaglia V S，Liu G. Effect of chromium and niobium doping on the morphology and electrochemical performance of high-voltage spinel LiNi0.5Mn1.5O4 cathode material ［J］. ACS Applied Materials & Interfaces，2016，8（14）： 9116.

［31］Madhu M，Venkateswara R A ，Mutyala S. La，Ni co-doping effect in LiMn2O4 on structural and electrochemical properties for lithium-ion batteries ［J］. Journal of Electronic Materials，2021，50（9）： 5141.

［32］Li M，Li Y，Guo Y J，Guo J M，Xiang M W，Bai W，Liu X F，Bai H L. A nano-truncated Ni/La doped manganese spinel material for high rate performance and long cycle life lithium-ion batteries ［J］. New Journal of Chemistry，2022，46（15）： 7078.

［33］Khedr A M，El-Metwaly F G，Abou-Sekkina M M. Solid state synthesis，fast and thermal neutrons irradiations effects，DC-electrical conductivity of La3+，Zr4+ double doped Nano lithium manganates for applications in Li-ion batteries ［J］. Journal of Molecular Liquids，2017，225： 863.

［34］Thirunakaran R，Ravikumar R，Vijayarani S，Gopukumar S，Sivashanmugam A. Molybdenum doped spinel as cathode material for lithium rechargeable cells ［J］. Energy Conversion and Management，2012，53（1）： 276.

［35］Jiang S J，Wang S，Li Y J，Hao S P，Xi X M，Liu S W，Xiong Y K，Zheng J C，Zhang P P. Structure and interface modification via Gd boosting excellent high-temperature electrochemical performance of LiMn2O4 ［J］. Materials Today Energy，2022，29： 101096.

［36］Venkateswara R A，Kumar B R，Ramarao S D. Structural，microstructural and electrochemical studies on LiMn2-x（GdAl）xO4 with spinel structure as cathode material for Li-ion batteries ［J］. Ceramics International，2018，44（13）： 15116.

［37］Venkateswara R A，Ranjith K B. Structural，electrical and electrochemical studies on doubly doped LiMn2−x（GdNi）xO4 cathode materials for Li-ion batteries ［J］. Materials Letters，2018，227： 250.

［38］Meng J Q，Zhang J J，Lu D H，Wei Z B，Yu F D，Wang Z B. Heterostructural Li1+xMn2-xO4 cathode materials of high performance for aqueous lithium-ion batteries ［J］. Ionics，2022，28（12）： 5405.

［39］Liang L Q，Xiang M W，Bai W，Guo J M，Su C W，Yang L Y，Bai H L，Liu X F. Electrochemical properties and kinetics of Li-Cu co-doping LiMn2O4 cathode materials ［J］. Journal of Materials Science： Materials in Electronics，2019，31（1）： 286.

［40］Llusco A，Rojas L，Ushak S，Grageda M. Potential use of magnesium industrial waste for synthesis of Li and Mg co-doped LiMn2O4 nanoparticles as cathode material for Li-ion batteries： effect of sintering temperature ［J］. Nano Research，2022，15（5）： 4500.

［41］Dai K，Mao J，Li Z，Zhai Y，Wang Z，Song X，Battaglia V，Liu G. Microsized single-crystal spinel LAMO for high-power lithium ion batteries synthesized via polyvinylpyrrolidone combustion method ［J］. Journal of Power Sources，2014，248： 22.

［42］Liu X P，Chen Q Q，Li Y W，Chen C，Xing X，Huang B，Yang J W，Xiao S H，Chen S J，Wang R H. LiMn2O4 cathode materials with excellent performances by synergistic enhancement of double-cation （Na+，Mg2+） doping and 3DG coating for power lithium-ion batteries ［J］. The Journal of Physical Chemistry C，2020，124（48）： 26106.

［43］Li B C，Wang M，Zhang Y X，Guo Q，Tian R N，Chen J J，Wang D J，Dong C L，Mao Z Y. Strengthening reversibility at high rate of spinel LiMn2O4 by aluminum and copper co-doping for lithium ion battery ［J］. Electrochimica Acta，2023，464： 142898.

［44］Angelopoulou P，Paloukis F，Słowik G，Wójcik G，Avgouropoulos G. Combustion-synthesized LixMn2O4-based spinel nanorods as cathode materials for lithium-ion batteries ［J］. Chemical Engineering Journal，2017，311： 191.

［45］Molenda M，Bakierska M，Majda D，Świętosławski M，Dziembaj R. Structural and electrochemical characterization of sulphur-doped lithium manganese spinel cathode materials for lithium ion batteries ［J］. Solid State Ionics，2015，272： 127.

［46］Kubicka M，Bakierska M，Świętosławski M，Chudzik K，Molenda M. The temperature effect on the electrochemical performance of sulfur-doped LiMn2O4 in Li-ion cells ［J］. Nanomaterials，2019，9（12）： 1722.

［47］Jiang Q Q，Liu D D，Zhang H，Wang S Y. Plasma-assisted sulfur doping of LiMn2O4 for high-performance lithium-ion batteries ［J］. The Journal of Physical Chemistry C，2015，119（52）： 28776.

［48］Bakierska M，Świętosławski M，Chudzik K，Lis M，Molenda M. Enhancing the lithium ion diffusivity in LiMn2O4-ySy cathode materials through potassium doping ［J］. Solid State Ionics，2018，317： 190.

［49］Bakierska M，Świętosławski M，Gajewska M，Kowalczyk A，Piwowarska Z，Chmielarz L，Dziembaj R，Molenda M. Enhancement of electrochemical performance of LiMn2O4 spinel cathode material by synergetic substitution with Ni and S ［J］. Materials，2016，9（5）： 366.

［50］Chudzik K，Lis M，Świętosławski M，Bakierska M，Gajewska M，Molenda M. Improving the performance of sulphur doped LiMn2O4 by carbon coating ［J］. Journal of Power Sources，2019，434： 226725.

［51］Chudzik K，Świętosławski M，Bakierska M，Kubicka M，Gajewska M，Molenda M. Surface modification and carbon coating effect on a high-performance K and S doped LiMn2O4 ［J］. Applied Surface Science，2020，531： 147138.

［52］Chudzik K，Świętosławski M，Bakierska M，Kubicka M，Natkański P，Kawałko J，Molenda M. Electrochemical properties of K and S doped LiMn2O4 studied by GITT and EIS ［J］. Electrochimica Acta，2021，373： 137901.

［53］Nyamaa O，Jeong H M，Kang G H，Kim J S，Goo K M，Baek I G，Yang J H，Nam T H，Noh J P. Enhanced LiMn2O4 cathode performance in lithium-ion batteries through synergistic cation and anion substitution ［J］. Materials Advances，2024，5（7）： 2872.

［54］Wang J L，Liu C J，Xu G L，Miao C，Wen M Y，Xu M B，Wang C J，Xiao W. Strengthened the structural stability of in-situ F− doping Ni-rich LiNi0.8Co0.15Al0.05O2 cathode materials for lithium-ion batteries ［J］. Chemical Engineering Journal，2022，438： 135537.

［55］Wang F C，Tian J K，Zhang H L. Synthesis，electrochemical performance of co-doped LiMn2O4 by Mg and F with one improved soild-state method ［J］. International Journal of Electrochemical Science，2014，9（8）： 4627.

［56］Li P，Luo S，Wang J C，Wang X，Tian Y，Li H，Wang Q，Zhang Y H，Liu X. Preparation and electrochemical properties of Al‐F co‐doped spinel LiMn2O4 single‐crystal material for lithium‐ion battery ［J］. International Journal of Energy Research，2021，45（15）： 21158.

Basic Information:

DOI：10.13373/j.cnki.cjrm.XY24080008

Chinese Library Classification Number:TF803.21

Citation Information:

It is well-known that lithium-ion batteries （LIBs） are recognized as one of the most appropriate and promising energy-storage systems，they are also being pursued intensively for transporting applications，including hybrid vehicles （HEVs） and pure electric vehicles （EVs）. However，existing commercial LIBs are the current limitation for the rapid development of both EVs and HEVs due to their limited energy densities and high price cost. Great efforts have been made to develop cathode materials with high voltage，high capacity，low cost，and excellent cycle performance. In this regard，lithium manganate （LiMn₂O₄） with spinel structure has been considered as one of the most promising cathode materials for the next generation high energy density LIBs owing to its high potential （4.1 V），relatively high theoretical capacity （148 mAh·g⁻¹），and abundance of the raw materials. At present，the large-scale commercialization applications of LiMn₂O₄ are plagued by its serious capacity degradation and structural instability during Li⁺ intercalation/de-intercalation process，particularly at higher C rates. Element doping is a widely acceptable modification approach to improve the structural stability of the bulk LiMn₂O₄. Bulk phase doping consists of lithium site，manganese site and oxygen site accor ding to the lattice position occupied by the doped element. Among them，the mainstream of doping studies is manganese site doping，which mainly includes Ni²⁺，Fe²⁺，Zn²⁺，Mg²⁺，Al³⁺，Co³⁺，Ti⁴⁺，etc. The results show that partial substitution of Mn³⁺ can effectively inhibit the structural deformation caused by Jahn-Teller effect，enhance the structural stability of the material，and then improve the cycle performance. Lithium site doping is the partial substitution of the doped element for the Li position in the LiMn₂O₄ structure. Na⁺ is usually used to replace part of Li⁺. Because the electrochemical activity of Na⁺ is worse than that of Li⁺，Na⁺ can remain in the three-dimensional channel of Li⁺ diffusion during the charging and discharging process，and play a role in supporting Li⁺ diffusion channel. Oxygen site doping is the substitution of doping elements such as S，Cl，F，etc. After F replaces O，the bond energy can be enhanced，thereby improving the stability of the crystal structure，and the lattice constant can be increased after Cl and S replace O，facilitating the diffusion of lithium ions. There have been reviews focusing on single element doping for LiMn₂O₄，while the development in the recent years still needs to be summarized，especially the research of double element doping. In this review，the research progress of two-element doped spinel lithium manganate materials in recent years was reviewed，and the future development trend of spinel lithium manganate material was also analyzed.