Sodium-ion batteries have emerged as a promising energy storage technology with global interest. However, the limited specific capacity of hard carbon, the primary anode material for sodium-ion batteries, restrains further improvement in energy density for full cells. In contrast, phosphorus-based anode materials have gained attention for high-performance sodium-ion batteries owing to their abundance and high theoretical specific capacity. The review summarizes some efficient strategies to improve structural stability and electrochemical performance by exploring the recent relevant literature. Black phosphorus can be easily prepared through mechanical methods and complexed with carbon materials such as graphene, multi-walled carbon nanotubes, and ketjen black. However, it is important to consider the formation of microscopic chemical bonds to enhance structural integrity and sodium storage reversibility. The chemical bonding between the surfaces of carbon material and black phosphorus plays a crucial role in achieving these advancements. In addition, the combination of conductive polymer and two-dimensional compounds with black phosphorus offers a pathway for optimizing material properties and electrode microstructures, further enhancing the electrochemical performance of sodium-ion batteries. Finally, the development prospect of black phosphorus-based anode material for sodium-ion batteries is proposed, highlighting their potential in advancing energy storage.
Keywords：sodium-ion battery
;
anode material
;
phosphorus carbon composite material
;
black phosphorus
ZHANG Ding. Research progress of black phosphorus-based anode materials for sodium-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(8): 2482-2490
Fig. 1
(a) Scheme for the structures of BPC composite；(b) TEM images of the BPC composite；(c)—(d) Cyclic performance diagram of BPC at different current densities；(e)—(f) Rate performance of a Na0.66Ni0.26Zn0.07Mn0.67O2/P cell[24]
黑磷是磷的三种异形体中最稳定的，它可以与白磷或红磷在一定的条件下相互转化。1914年，Bridgman[15]在200 ℃下研究高压(1.2 GPa)条件对白磷熔点的影响时获得了黑磷。黑磷有正交、菱形、简单立方和无定形四种晶体结构，在常温常压下，黑磷晶格具备正交结构[16]，每个磷原子与三个相邻的磷原子共价结合。由于sp3杂化，原子层中的磷原子不共面[17]，黑磷的空间群为Cmca，a=3.313Å，b=10.473Å，c=4.374Å，它具有高载流子迁移率、高理论容量、良好的热稳定性以及高度各向异性[18-19]。在与其他二维材料异质堆叠时，黑磷表现出了光致发光猝灭效应[20]。作为二次电池的负极材料，得益于它出色的高电荷迁移率，使得黑磷在储能电极材料时表现出独特的电子特性。研究发现，低层黑磷的电荷迁移率与厚度有关[18, 21]。由于范德华相互作用的影响，黑磷的各层堆叠在一起，这使得黑磷较为容易通过机械的方法获得单层结构的黑磷[22]。自从2014年二维黑磷材料用在晶体管中以来[18]，科研人员对二维黑磷的应用开展了多方探讨。作为一种二维半导体材料，其带隙可调、导电性好；而且也具有超高的储钠理论容量。Hembram等人[23]基于第一性原理计算提出了黑磷钠化的原子机制，黑磷的层状结构一直保持到Na0.25P的组成，当Na含量超过0.25时，插层过程转变成合金化过程。当在Na0.25P结构中加入两个以上的Na原子形成Na0.28P结构时，P—P键的解离过程开始，进一步钠化作用最终会导致层状Na x P结构形成非晶相。随着钠化的进一步进行，大部分哑铃型P2会变成孤立的P原子。虽然黑磷的储钠历程与红磷不同，但是最终产物相同，因此具有同样的理论储钠比容量(2596 mAh/g)。
Fig. 2
(a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g[25];(b) The specific capacity of 4-RBP at different current density[25]; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids[26];(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g[26]; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g[29]
Fig. 3
(a) Schematic description of the BP/rGO synthesis; (b) Cycling performance of the BP/rGO anodes at charge and discharge current densities of 1 and 40 A/g [31]
Fig. 4
(a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities[32]; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes[33]; (c) Rct of BP, BP-G, and BP-G/PANI[33]; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling[33]; (e) Cyclic performance of BP-G/PANI at different current densities[33]
导电高分子材料与黑磷复合可以增强钠离子电池的循环性能和放电比容量，而高分子材料也可以作为电极黏结剂，缓冲黑磷的体积膨胀，从而改善钠离子电池的性能。在2021年，Callegari等人[34]开发出了新型的脲嘧啶酮(UPy)-远螺旋体系和与聚(环氧乙烷)相关的聚合物(UPyPEG n UPy)作为黏结剂。具有多重氢键的自主自愈的黏结剂，能有效地克服黑磷由体积膨胀/收缩引起机械损伤而使容量急剧衰减的问题，该种聚合物可以协助阳极内的钠离子传输，并且降低了电荷转移电阻，从而增强电化学动力学。基于此种黏结剂具有更好的附着力、缓冲性能和自发损伤修复的能力，使SIBs在电流密度高于3.5 A/g时仍然能正常工作，这种黏结剂虽然对SIBs电极的循环性能和稳定性都有显著的有益影响，但是还需要额外的工作来满足SIBs的商业要求。
2.3 黑磷与新型二维材料构成的复合材料
利用化学性质稳定的二维盖层形成的异质结构可有效抑制黑磷表面降解。在2020年，Guo等人[35]通过将磷烯和Ti3C2T x MXene胶体水溶液以一定质量比制备了BP/MXene复合材料，互补的二维(2D)材料堆叠成混合结构，并将其用作钠离子储能材料。二维异质结构Ti3C2T x MXene中的氟末端与钠形成NaF，促进了电子和钠离子的迁移，并且含有氟末端的MXene有利于形成稳定的SEI层，SEI层可以有效地抑制活性物质与电解质之间的反应，提高了库仑效率。通过密度泛函理论(DFT)计算表明，在磷烯/MXene异质结构中，特别是在磷烯/Ti3C2F2中，钠的扩散动力学也显著提升。
Fig. 5
(a) Schematic explanation for the MoS2 nanosheets on a BP nanosheets support in the MoS2/BP composite; (b) Cycling stability of MoS2/BP at 1 A/g in comparison with MoS2 and BP electrodes; (c) Long-term cycling stability of the MoS2/BP composite at 10 A/g; (d) Anti-static charge-discharge performance of full battery at 0.2 A/g [37]
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<strong>(a) Scheme for the structures of BPC composite</strong>；<strong>(b) TEM images of the BPC composite</strong>；<strong>(c)</strong>—<strong>(d) Cyclic performance diagram of BPC at different current densities</strong>；<strong>(e)</strong>—<strong>(f) Rate performance of a Na<sub>0.66</sub>Ni<sub>0.26</sub>Zn<sub>0.07</sub>Mn<sub>0.67</sub>O<sub>2</sub>/P cell</strong><sup>[<xref ref-type="bibr" rid="R24">24</xref>]</sup>Fig. 1
黑磷是磷的三种异形体中最稳定的，它可以与白磷或红磷在一定的条件下相互转化.1914年，Bridgman[15]在200 ℃下研究高压(1.2 GPa)条件对白磷熔点的影响时获得了黑磷.黑磷有正交、菱形、简单立方和无定形四种晶体结构，在常温常压下，黑磷晶格具备正交结构[16]，每个磷原子与三个相邻的磷原子共价结合.由于sp3杂化，原子层中的磷原子不共面[17]，黑磷的空间群为Cmca，a=3.313Å，b=10.473Å，c=4.374Å，它具有高载流子迁移率、高理论容量、良好的热稳定性以及高度各向异性[18-19].在与其他二维材料异质堆叠时，黑磷表现出了光致发光猝灭效应[20].作为二次电池的负极材料，得益于它出色的高电荷迁移率，使得黑磷在储能电极材料时表现出独特的电子特性.研究发现，低层黑磷的电荷迁移率与厚度有关[18, 21].由于范德华相互作用的影响，黑磷的各层堆叠在一起，这使得黑磷较为容易通过机械的方法获得单层结构的黑磷[22].自从2014年二维黑磷材料用在晶体管中以来[18]，科研人员对二维黑磷的应用开展了多方探讨.作为一种二维半导体材料，其带隙可调、导电性好；而且也具有超高的储钠理论容量.Hembram等人[23]基于第一性原理计算提出了黑磷钠化的原子机制，黑磷的层状结构一直保持到Na0.25P的组成，当Na含量超过0.25时，插层过程转变成合金化过程.当在Na0.25P结构中加入两个以上的Na原子形成Na0.28P结构时，P—P键的解离过程开始，进一步钠化作用最终会导致层状Na x P结构形成非晶相.随着钠化的进一步进行，大部分哑铃型P2会变成孤立的P原子.虽然黑磷的储钠历程与红磷不同，但是最终产物相同，因此具有同样的理论储钠比容量(2596 mAh/g). ...
... [24]Fig. 1
黑磷是磷的三种异形体中最稳定的，它可以与白磷或红磷在一定的条件下相互转化.1914年，Bridgman[15]在200 ℃下研究高压(1.2 GPa)条件对白磷熔点的影响时获得了黑磷.黑磷有正交、菱形、简单立方和无定形四种晶体结构，在常温常压下，黑磷晶格具备正交结构[16]，每个磷原子与三个相邻的磷原子共价结合.由于sp3杂化，原子层中的磷原子不共面[17]，黑磷的空间群为Cmca，a=3.313Å，b=10.473Å，c=4.374Å，它具有高载流子迁移率、高理论容量、良好的热稳定性以及高度各向异性[18-19].在与其他二维材料异质堆叠时，黑磷表现出了光致发光猝灭效应[20].作为二次电池的负极材料，得益于它出色的高电荷迁移率，使得黑磷在储能电极材料时表现出独特的电子特性.研究发现，低层黑磷的电荷迁移率与厚度有关[18, 21].由于范德华相互作用的影响，黑磷的各层堆叠在一起，这使得黑磷较为容易通过机械的方法获得单层结构的黑磷[22].自从2014年二维黑磷材料用在晶体管中以来[18]，科研人员对二维黑磷的应用开展了多方探讨.作为一种二维半导体材料，其带隙可调、导电性好；而且也具有超高的储钠理论容量.Hembram等人[23]基于第一性原理计算提出了黑磷钠化的原子机制，黑磷的层状结构一直保持到Na0.25P的组成，当Na含量超过0.25时，插层过程转变成合金化过程.当在Na0.25P结构中加入两个以上的Na原子形成Na0.28P结构时，P—P键的解离过程开始，进一步钠化作用最终会导致层状Na x P结构形成非晶相.随着钠化的进一步进行，大部分哑铃型P2会变成孤立的P原子.虽然黑磷的储钠历程与红磷不同，但是最终产物相同，因此具有同样的理论储钠比容量(2596 mAh/g). ...
... [25]；(b) 4-RBP在不同电流密度下的比容量[25]；(c) NTO/C-BP杂化示意图[26]；(d) NTO/C和NTO/C-BP的电化学测试：在200 mA/g时的循环性能[26]；(e) 在100 mA/g、200 mA/g、500 mA/g的电流密度下循环100次的循环性能[29](a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>;(b) The specific capacity of 4-RBP at different current density<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>;(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g<sup>[<xref ref-type="bibr" rid="R29">29</xref>]</sup>Fig. 2
... [25]；(c) NTO/C-BP杂化示意图[26]；(d) NTO/C和NTO/C-BP的电化学测试：在200 mA/g时的循环性能[26]；(e) 在100 mA/g、200 mA/g、500 mA/g的电流密度下循环100次的循环性能[29](a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>;(b) The specific capacity of 4-RBP at different current density<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>;(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g<sup>[<xref ref-type="bibr" rid="R29">29</xref>]</sup>Fig. 2
... [25];(b) The specific capacity of 4-RBP at different current density[25]; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids[26];(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g[26]; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g[29]Fig. 2
... [25]; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids[26];(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g[26]; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g[29]Fig. 2
(a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>;(b) The specific capacity of 4-RBP at different current density<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>;(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g<sup>[<xref ref-type="bibr" rid="R29">29</xref>]</sup>Fig. 2
... [26]；(e) 在100 mA/g、200 mA/g、500 mA/g的电流密度下循环100次的循环性能[29](a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>;(b) The specific capacity of 4-RBP at different current density<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>;(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g<sup>[<xref ref-type="bibr" rid="R29">29</xref>]</sup>Fig. 2
... [26];(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g[26]; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g[29]Fig. 2
(a) Specific capability and coulombic efficiency of the 4-RBP anode at current density of 1 A/g<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>;(b) The specific capacity of 4-RBP at different current density<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup>; (c) Schematic illustration of the fabrication of the NTO/C-BP hybrids<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>;(d) Electrochemical measurements of NTO/C and NTO/C-BP: Cycling performance at 200 mA/g<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>; (e) Performance of 100 cycles at current densities of 100 mA/g, 200 mA/g, and 500 mA/g<sup>[<xref ref-type="bibr" rid="R29">29</xref>]</sup>Fig. 2
... [31](a) Schematic description of the BP/rGO synthesis; (b) Cycling performance of the BP/rGO anodes at charge and discharge current densities of 1 and 40 A/g <sup>[<xref ref-type="bibr" rid="R31">31</xref>]</sup>Fig. 3<strong>2.2</strong> 黑磷<strong>/</strong>导电高分子复合材料
... [32]；(b) BP-G和BP-G/PANI电极的钠化示意图[33]；(c) BP、BP-G和BP-G/PANI的电荷转移电阻[33]；(d) 循环前后BP-G/PANI和BP-G电极的横截面SEM图像[33]；(e) 在不同电流密度下BP-G/PANI的循环性能[33](a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities<sup>[<xref ref-type="bibr" rid="R32">32</xref>]</sup>; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (c) Rct of BP, BP-G, and BP-G/PANI<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (e) Cyclic performance of BP-G/PANI at different current densities<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig. 4
... [32]; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes[33]; (c) Rct of BP, BP-G, and BP-G/PANI[33]; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling[33]; (e) Cyclic performance of BP-G/PANI at different current densities[33]Fig. 4
(a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities<sup>[<xref ref-type="bibr" rid="R32">32</xref>]</sup>; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (c) Rct of BP, BP-G, and BP-G/PANI<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (e) Cyclic performance of BP-G/PANI at different current densities<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig. 4
... [33]；(d) 循环前后BP-G/PANI和BP-G电极的横截面SEM图像[33]；(e) 在不同电流密度下BP-G/PANI的循环性能[33](a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities<sup>[<xref ref-type="bibr" rid="R32">32</xref>]</sup>; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (c) Rct of BP, BP-G, and BP-G/PANI<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (e) Cyclic performance of BP-G/PANI at different current densities<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig. 4
... [33]；(e) 在不同电流密度下BP-G/PANI的循环性能[33](a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities<sup>[<xref ref-type="bibr" rid="R32">32</xref>]</sup>; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (c) Rct of BP, BP-G, and BP-G/PANI<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (e) Cyclic performance of BP-G/PANI at different current densities<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig. 4
... [33](a) Cyclic performance of E-BP/PEDOT and E-BP electrodes at different current densities<sup>[<xref ref-type="bibr" rid="R32">32</xref>]</sup>; (b) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (c) Rct of BP, BP-G, and BP-G/PANI<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>; (e) Cyclic performance of BP-G/PANI at different current densities<sup>[<xref ref-type="bibr" rid="R33">33</xref>]</sup>Fig. 4
... [33]; (c) Rct of BP, BP-G, and BP-G/PANI[33]; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling[33]; (e) Cyclic performance of BP-G/PANI at different current densities[33]Fig. 4
... [33]; (d) SEM images of cross section of BP-G/PANI and BP-G electrodes before and after cycling[33]; (e) Cyclic performance of BP-G/PANI at different current densities[33]Fig. 4
... 导电高分子材料与黑磷复合可以增强钠离子电池的循环性能和放电比容量，而高分子材料也可以作为电极黏结剂，缓冲黑磷的体积膨胀，从而改善钠离子电池的性能.在2021年，Callegari等人[34]开发出了新型的脲嘧啶酮(UPy)-远螺旋体系和与聚(环氧乙烷)相关的聚合物(UPyPEG n UPy)作为黏结剂.具有多重氢键的自主自愈的黏结剂，能有效地克服黑磷由体积膨胀/收缩引起机械损伤而使容量急剧衰减的问题，该种聚合物可以协助阳极内的钠离子传输，并且降低了电荷转移电阻，从而增强电化学动力学.基于此种黏结剂具有更好的附着力、缓冲性能和自发损伤修复的能力，使SIBs在电流密度高于3.5 A/g时仍然能正常工作，这种黏结剂虽然对SIBs电极的循环性能和稳定性都有显著的有益影响，但是还需要额外的工作来满足SIBs的商业要求. ...
1
... 利用化学性质稳定的二维盖层形成的异质结构可有效抑制黑磷表面降解.在2020年，Guo等人[35]通过将磷烯和Ti3C2T x MXene胶体水溶液以一定质量比制备了BP/MXene复合材料，互补的二维(2D)材料堆叠成混合结构，并将其用作钠离子储能材料.二维异质结构Ti3C2T x MXene中的氟末端与钠形成NaF，促进了电子和钠离子的迁移，并且含有氟末端的MXene有利于形成稳定的SEI层，SEI层可以有效地抑制活性物质与电解质之间的反应，提高了库仑效率.通过密度泛函理论(DFT)计算表明，在磷烯/MXene异质结构中，特别是在磷烯/Ti3C2F2中，钠的扩散动力学也显著提升. ...
... [37](a) Schematic explanation for the MoS<sub>2</sub> nanosheets on a BP nanosheets support in the MoS<sub>2</sub>/BP composite; (b) Cycling stability of MoS<sub>2</sub>/BP at 1 A/g in comparison with MoS<sub>2</sub> and BP electrodes; (c) Long-term cycling stability of the MoS<sub>2</sub>/BP composite at 10 A/g; (d) Anti-static charge-discharge performance of full battery at 0.2 A/g<sup> [<xref ref-type="bibr" rid="R37">37</xref>]</sup>Fig. 5
