P2-O3复合相富锂锰基正极材料的合成及性能研究

doi:10.19799/j.cnki.2095-4239.2020.0021

摘要/Abstract

摘要：

为了解决高比能富锂材料电压衰退、首圈库仑效率低、倍率性能差等问题，本文通过简单的固相烧结法合成P2-O3复合相富锂正极材料。该材料利用P2相在首次充放电过程中转化为O2相，避免过渡金属迁移，有效地降低了循环过程中的电压衰退，极大地提高了首圈库仑效率和倍率性能。电化学性能测试表明，在2.0~4.6 V以0.1 C（1 C=200 mA/g）电流进行充放电，P2-O3复合相富锂正极材料可以提供高于290 mA·h/g的比容量，首圈库仑效率高达97%。1 C放电比容量约为240 mA·h/g，100圈容量保持率接近80%；100圈平均电压衰退小于170 mV。该复合相富锂正极材料合成制备简单；在2.0~4.6V电压范围内，实现传统富锂材料在2.0~4.8 V下的高容量，这大大促进了富锂材料与商用电解液的匹配；此外，循环性能相对良好，电压衰退也得到了一定的抑制，有力地推动了富锂材料在电动汽车市场上的应用。

关键词: 复合相, 富锂锰基正极材料, 电压衰退, 首圈库仑效率

Abstract:

To solve the common issues of voltage decay, low initial coulombic efficiency, and poor rate performance that occur in high-energy lithium-rich cathode materials, a P2-O3 composite-phase cathode material was synthesized by the simple solid-state method. During the first charging and discharging process, this material experienced P2-O2 phase transition, and the O2 phase prevented transition metal migration; thus, voltage decay was effectively mitigated. This P2-O3 composite-phase cathode material delivered a specific capacity of over 290 mA·h/g with an initial coulombic efficiency of 97% under a current density of 0.1C (1C = 200 mA/g) at 2.0—4.6 V. When charged at 200 mA/g, this material released a capacity of about 240 mA·h/g. After 100 cycles, the capacity retention was approximately 80% and the voltage loss was less than 170 mV. This material is easy to synthesize. At 2.0—4.6 V, it delivered a capacity as high as that of traditional lithium-rich materials tested at 2.0—4.8 V, which greatly promotes the adaptation of lithium-rich materials with commercial electrolytes. Furthermore, the cycle performance is relatively optimum and the voltage decay is suppressed to some extent, which strongly promotes the practical application of lithium-rich materials in the electric vehicles market.

Key words: composite phase, Li-rich Mn-based cathode material, voltage decay, initial coulombic efficiency

中图分类号:

TM 912.9

张建宇, 鲁理平, 于志辉, 宋进, 夏定国. P2-O3复合相富锂锰基正极材料的合成及性能研究[J]. 储能科学与技术, 2020, 9(2): 346-352.

ZHANG Jianyu, LU Liping, YU Zhihui, SONG Jin, XIA Dingguo. Synthesis and performance of P2-O3 composite-phase Li-rich Mn-based cathode materials[J]. Energy Storage Science and Technology, 2020, 9(2): 346-352.

图/表 7

图1

图2

图3

图4

图5

图6

表1

参考文献 40

1	陈晓轩, 李晟, 胡泳钢, 等 . 锂离子电池三元层状氧化物正极材料失效模式分析[J]. 储能科学与技术, 2019, 8(6): 1003-1016.
	CHEN Xiaoxuan , LI Sheng , HU Yonggang , et al . Failure mechanism of Li₁₊ _x (NCM)_1- _x O₂ layered oxide cathode material during capacity degradation[J]. Energy Storage Science and Technology, 2019, 8(6): 1003-1016.
2	ARIZA M J , JONES D J , ROZIÈRE J , et al . Probing the local structure and the role of protons in lithium sorption processes of a new lithium-rich manganese oxide[J]. Chemistry of Materials, 2006, 18(7): 1885-1890.
3	SONG C , FENG W , SHI Z , et al . Effect of drying temperature on properties of lithium-rich manganese-based materials in sol-gel method[J]. Ionics, 2019: 1-8.
4	KIM T , SONG B , LUNT A J G , et al . Operando X-ray absorption spectroscopy study of atomic phase reversibility with wavelet transform in the lithium-rich manganese based oxide cathode[J]. Chemistry of Materials, 2016, 28(12): 4191-4203.
5	ZHANG Z , LIU C , FENG C , et al . Breaking the local symmetry of LiCoO₂via atomic doping for efficient oxygen evolution[J]. Nano Letters, 2019, 19(12): 8774-8779.
6	OHZUKU T , UEDA A , NAGAYAMA M , et al . Comparative study of LiCoO₂, LiNi₁₂Co₁₂O₂ and LiNiO₂ for 4 volt secondary lithium cells[J]. Electrochimica Acta, 1993, 38(9): 1159-1167.
7	OKUBO M , HOSONO E , KIM J , et al . Nanosize effect on high-rate Li-ion intercalation in LiCoO₂ electrode[J]. Journal of the American Chemical Society, 2007, 129(23): 7444-7452.
8	THACKERAY M M , JOHNSON P J , DE PICCIOTTO L A , et al . Electrochemical extraction of lithium from LiMn₂O₄ [J]. Materials Research Bulletin, 1984, 19(2): 179-187.
9	LEE H W, MURALIDHARAN P , RUFFO R , et al . Ultrathin spinel LiMn₂O₄ nanowires as high power cathode materials for Li-ion batteries[J]. Nano Letters, 2010, 10(10): 3852-3856.
10	HUANG W , WANG G , LUO C , et al . Controllable growth of LiMn₂O₄ by carbohydrate-assisted combustion synthesis for high performance Li-ion batteries[J]. Nano Energy, 2019, 64: doi: 10.1016/j.nanoen.2019.103936.
11	DAIGLE J C , BARRAY F , GAGNON C , et al . Amphiphilic latex as a water-based binder for LiFePO₄ cathode[J]. Journal of Power Sources, 2019, 415: 172-178.
12	HUANG H , YIN S C , NAZAR L F . Approaching theoretical capacity of LiFePO₄ at room temperature at high rates[J]. Electrochemical and Solid-State Letters, 2001, 4(10): A170-A172.
13	XIE H M , WANG R S , YING J R , et al . Optimized LiFePO₄-polyacene cathode material for lithium-ion batteries[J]. Advanced Materials, 2006, 18(19): 2609-2613.
14	DENG Z Q , MANTHIRAM A . Influence of cationic substitutions on the oxygen loss and reversible capacity of lithium-rich layered oxide cathodes[J]. The Journal of Physical Chemistry C, 2011, 115(14): 7097-7103.
15	ZHENG F , YANG C , XIONG X , et al . Nanoscale surface modification of lithium-rich layered-oxide composite cathodes for suppressing voltage fade[J]. Angewandte Chemie International Edition, 2015, 54(44): 13058-13062.
16	YANG X , WANG D , YU R , et al . Suppressed capacity/voltage fading of high-capacity lithium-rich layered materials via the design of heterogeneous distribution in the composition[J]. Journal of Materials Chemistry A, 2014, 2(11): 3899-3911.
17	ZHANG S , GU H , PAN H , et al . A novel strategy to suppress capacity and voltage fading of Li- and Mn-rich layered oxide cathode material for lithium-ion batteries[J]. Advanced Energy Materials, 2017, 7(6): doi: 10.1002/aenm.201601066.
18	ZOU W , XIA F J , SONG J P , et al . Probing and suppressing voltage fade of Li-rich Li_{1. 2}Ni_{0. 13}Co_{0. 13}Mn_{0. 54}O₂ cathode material for lithium-ion battery[J]. Electrochimica Acta, 2019, doi: 10.1016/j.electacta.2019.06.119 . doi: 10.1016/j.electacta.2019.06.119
19	MARTHA S K , NANDA J , VEITH G M , et al . Electrochemical and rate performance study of high-voltage lithium-rich composition: Li_1.2Mn_0.525Ni_0.175Co_{0. 1}O₂ [J]. Journal of Power Sources, 2012, 199: 220-226.
20	GENT W E , LIM K, LIANG Y , et al . Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides[J]. Nature Communications, 2017, 8(1):doi: 10.1038/s41467-017-02041-x .
21	AVAN BOMMEL , DAHN J R . Kinetics study of the high potential range of lithium-rich transition-metal oxides for lithium-ion batteries by electrochemical methods[J]. Electrochemical and Solid-State Letters, 2010, 13(5): A62-A64.
22	XU M , CHEN Z , LI L , et al . Highly crystalline alumina surface coating from hydrolysis of aluminum isopropoxide on lithium-rich layered oxide[J]. Journal of Power Sources, 2015, 281: 444-454.
23	YU R , WANG G , LIU M , et al . Mitigating voltage and capacity fading of lithium-rich layered cathodes by lanthanum doping[J]. Journal of Power Sources, 2016, 335: 65-75.
24	OH P, OH S M, LI W , et al . High-performance heterostructured cathodes for lithium-ion batteries with a Ni-rich layered oxide core and a Li-rich layered oxide shell[J]. Advanced Science, 2016, 3(11): doi: 10.1002/advs.201600184.
25	BETTGE M , LI Y , GALLAGHER K , et al . Voltage fade of layered oxides: Its measurement and impact on energy density[J]. Journal of the Electrochemical Society, 2013, 160(11): A2046-A2055.
26	HU E Y , YU X Q , LIN R Q , et al . Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release[J]. Nature Energy, 2018, 3(8): 690-698.
27	BLOOM I , TRAHEY L , ABOUIMRANE A , et al . Effect of interface modifications on voltage fade in 0.5Li₂MnO₃ ·0.5LiMn_0.375Ni_0.375Co_0.25O₂ cathode materials[J]. Journal of Power Sources, 2014, 249: 509-514.
28	ZHENG F , YANG C , XIONG X , et al . Nanoscale surface modification of lithium-rich layered-oxide composite cathodes for suppressing voltage fade[J]. Angew Chem. Int. Ed. Engl., 2015, 54 (44): 13058-13062.
29	GU M , BELHAROUAK I , ZHENG J M , et al . Formation of the spinel phase in the layered composite cathode used in Li-ion batteries[J]. ACS Nano, 2013, 7 (1): 760-767.
30	ITO A, SHODA K , SATO Y , et al . Direct observation of the partial formation of a framework structure for Li-rich layered cathode material Li[Ni_0.17Li_0.2Co_0.07Mn_0.56]O₂ upon the first charge and discharge[J]. Journal of Power Sources, 2011, 196 (10): 4785-4790.
31	SATHIYA M , ABAKUMOV A M , FOIX D , et al . Origin of voltage decay in high-capacity layered oxide electrodes[J]. Nat. Mater., 2015, 14 (2): 230-238.
32	PAULSEN J M , THOMAS C L , DAHN J R . Layered Li-Mn-oxide with the O2 structure: A cathode material for Li-ion cells which does not convert to spinel[J]. Journal of the Electrochemical Society, 1999, 146 (10): 3560-3565.
33	ZUO Y , LI B , JIANG N , et al . A high-capacity O2-type Li-rich cathode material with a single-layer Li₂MnO₃ superstructure[J]. Advanced Materials, 2018, 30(16): doi: 10.1002/adma.201707255.
34	GUO S , LIU P , YU H , et al . A layered P2- and O3-type composite as a high-energy cathode for rechargeable sodium-ion batteries[J]. Angewandte Chemie International Edition, 2015, 54(20): 5894-5899.
35	YABUUCHI N , HARA R , KAJIYAMA M , et al . New O2/P2-type li-excess layered manganese oxides as promising multi-functional electrode materials for rechargeable Li/Na batteries[J]. Advanced Energy Materials, 2014, 4(13): 13072-13072.
36	ZHANG X H , PANG W L , WAN F , et al . P2-Na_2/3Ni_1/3Mn_5/9Al_1/9O₂microparticles as superior cathode material for sodium-ion batteries: Enhanced properties and mechanism via graphene connection[J]. ACS Applied Materials & Interfaces, 2016, 8(32): 20650-20659.
37	DUFFORT V , TALAIE E , BLACK R , et al . Uptake of CO₂ in layered P2-Na_0.67Mn_0.5Fe_0.5O₂: Insertion of carbonate anions[J]. Chemistry of Materials, 2015, 27(7): 2515-2524.
38	QING R , SHI J , XIAO D , et al . Cathode materials: Enhancing the kinetics of Li-rich cathode materials through the pinning effects of gradient surface Na⁺ doping[J]. Adv. Energy Mater.,2016, 6(6): 1501914-1501922.
39	DING Z , FENG Y , JI R , et al . Improving the electrochemical cyclability of lithium manganese orthosilicate through the pillaring effects of gradient Na substitution[J]. Journal of Power Sources, 2017, 349: 18-26.
40	ZHAI N S , LI M W , WANG W L , et al . The application of the eIS in Li-ion batteries measurement[J]. Journal of Physics: Conference Series, 2006, 48: 1157-1161.

样品	R _s	R _SEI	R _CT
Na-LMNC	3.174	25.47	6.867
Li_1.2Mn_0.54Ni_0.13Co_0.13O₂	3.321	80.59	281.4

[1]	李钰颖, 魏雯珍, 李琦, 吴玉庭. 可用于低中温热能储存的四元硝酸盐/埃洛石/石墨定型复合材料的制备与研究[J]. 储能科学与技术, 2022, 11(3): 1044-1051.
[2]	安治国, 张显, 祝惠, 张春杰. 蜂窝状CPCM/水冷复合式圆柱型锂电池散热性能[J]. 储能科学与技术, 2022, 11(1): 211-220.
[3]	王海民, 王寓非, 胡峰. 石墨-石蜡复合相变材料的圆柱型动力电池组热管理性能[J]. 储能科学与技术, 2021, 10(1): 210-217.
[4]	徐众, 侯静, 李军, 吴恩辉, 黄平, 唐亚兰. 不同粒径活性炭/肉豆蔻酸复合相变材料[J]. 储能科学与技术, 2021, 10(1): 177-189.
[5]	邓婷婷, 蔡颖玲. 笼屉式水箱中膨胀石墨对石蜡熔化和凝固过程的影响[J]. 储能科学与技术, 2021, 10(1): 190-197.
[6]	叶闻杰, 杨肖, 孙富华, 杨冬梅, 杜炜, 杨波, 刘杨, 王启扬. 基于微通道平板换热器的相变材料放热性能影响研究[J]. 储能科学与技术, 2020, 9(6): 1747-1754.
[7]	刘丽辉, 莫雅菁, 孙小琴, 李杰, 李传常, 谢宝姗. 纳米增强型复合相变材料的传热特性[J]. 储能科学与技术, 2020, 9(4): 1105-1112.
[8]	徐众, 侯静, 万书权, 李军, 吴恩辉, 刘黔蜀, 甘鑫. 金属泡沫/石蜡复合相变材料的制备及热性能研究[J]. 储能科学与技术, 2020, 9(1): 109-116.
[9]	房满庭, 章学来, 纪珺, 华维三, 刘彪, 王绪哲. 水合盐复合相变材料的研究进展[J]. 储能科学与技术, 2019, 8(4): 709-717.
[10]	徐众, 黄平, 吴恩辉, 侯静, 李军, 刘黔蜀. 膨胀石墨/石蜡复合相变材料的电阻率分析[J]. 储能科学与技术, 2019, 8(2): 371-378.
[11]	李雨, 赵慧春, 白莹, 吴锋, 吴川. 高能量密度层状富锂锰基正极材料的改性研究进展[J]. 储能科学与技术, 2018, 7(3): 394-403.
[12]	张叶龙1，宋鹏飞1，周伟1，王刚1，许永1，翁立奎1，冷光辉2，丁玉龙2. 基于复合相变储热材料的电热储能系统[J]. 储能科学与技术, 2017, 6(6): 1250-.
[13]	李传1，司艳阳2，冷光辉1，许永2，丁玉峰2，翁立奎2，丁玉龙1. 高温复合相变材料储热电暖器的储热性能[J]. 储能科学与技术, 2017, 6(4): 739-747.
[14]	朱教群，宋轶，周卫兵，刘凤利. 基于碳材料的有机复合相变材料导热增强研究进展[J]. 储能科学与技术, 2017, 6(2): 213-222.
[15]	郭茶秀1，蔡宏伟2. 低温辐射供暖复合相变墙体热性能分析[J]. 储能科学与技术, 2016, 5(4): 539-544.