Formation of oxygen vacancy clusters in Li-rich Mn-based cathode Materials of lithium-ion batteries: First-principles calculations

Shi Xiao-Hong; Hou Bin-Peng; Li Zhi-Shuo; Chen Jing-Jin; Shi Xiao-Wen; Zhu Zi-Zhong

doi:10.7498/aps.72.20222300

Abstract

Using the first-principles method, the formation energy values of O-vacancy clusters of two Li-rich Mn-based ternary cathode materials of lithium ion battery with different amounts of nickel , i.e. Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ (space group $R\bar{3}m)$ and Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ (space group C2/m), are calculated. Results show that the formation energy of oxygen vacancy cluster of the material with less nickel content Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ can be always higher than that of the material Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ with higher nickel content. This indicates that the oxygen vacancy clusters are more likely to form in cathode material with higher nickel content. The formation energy of the oxygen vacancy cluster near the transition metal is always greater than that near the lithium ion, indicating that the removal of oxygen tends to occur near the Li ion. Lower temperature and higher partial pressure can increase the formation energy of oxygen vacancy cluster, and therefore inhibit the formation of oxygen vacancy cluster. In addition, the formation energy values of oxygen vacancy clusters with the transition metals in the materials replaced by other transition metals (i.e., Ti and Mo) are also calculated. The results show that, in addition to the case of Ni replaced by Ti near the double oxygen vacancies near the Li-ion in Li_1.2Ni_0.32Co_0.04Mn_0.44O₂, all the remaining cases of the transition metals Ni or Mn replaced by Ti or Mo always increase the formation energy of the O-vacancy cluster. Therefore, the doping should be able to inhibit the loss of oxygen and improve the structural stability of material.

Keywords:

Authors and contacts

1.
College of Physical Science and Technology, Xiamen University, Xiamen 361005, China
2.
Hongzhiwei Technology (Shanghai) Co. Ltd., Shanghai 200120, China

Corresponding author: Zhu Zi-Zhong, zzhu@xmu.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2016YFA0202601).

FullText HTML : translate this paragraph

References

[1]	Dunn B, Kamath H, Tarascon J M 2011 Science 334 928 Google Scholar
[2]	Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D 2011 Energy Environ. Sci. 4 3243 Google Scholar
[3]	Nitta N, Wu F, Lee J T, Yushin G 2015 Mater. Today 18 252 Google Scholar
[4]	Yuan L X, Wang Z H, Zhang W X, Hu X L, Chen J T, Huang Y H, Goodenough J B 2011 Energy Environ. Sci. 4 269 Google Scholar
[5]	Liu J L, Hou M Y, Yi J, Guo S S, Wang C X, Xia Y Y 2014 Energy Environ. Sci. 7 705 Google Scholar
[6]	Csernica P M, Kalirai S S, Gent W E, Lim K, Yu Y S, Liu Y, Ahn S J, Kaeli E, Xu X, Stone K H, Marshall A F, Sinclair R, Shapiro D A, Toney M F, Chueh W C 2021 Nat. Energy 6 642 Google Scholar
[7]	Hu E Y, Yu X Q, Lin R Q, Bi X X, Lu J, Bak S M, Nam K W, Xin H L, Jaye C, Fischer D A, Amine K, Yang X Q 2018 Nat. Energy 3 690 Google Scholar
[8]	Zhu Z, Yu D W, Yang Y, Su C, Huang Y M, Dong Y H, Waluyo I, Wang B M, Hunt A, Yao X H, Lee J, Xue W J, Li J 2019 Nat. Energy 4 1049 Google Scholar
[9]	Yan P, Zheng J, Tang Z K, Devaraj A, Chen G, Amine K, Zhang J G, Liu L M, Wang C 2019 Nat. Nanotechnol. 14 602 Google Scholar
[10]	Lee E, Persson K A 2014 Adv. Energy Mater. 4 1400498 Google Scholar
[11]	Hoang K 2015 Phys. Rev. Appl. 3 024013 Google Scholar
[12]	史晓红, 陈京金, 曹昕睿, 吴顺情, 朱梓忠 2022 物理学报 71 178202 Google Scholar Shi X H, Chen J J, Cao X R, Wu S Q, Zhu ZZ 2022 Acta Phy. Sin. 71 178202 Google Scholar
[13]	Michaud-Rioux V, Zhang L, Guo H 2016 J. Comput. Phys. 307 593 Google Scholar
[14]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[15]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[16]	Dudarev S L, Botton G A, Savrasov S Y, Humphreys C J, Sutton A P 1998 Phys. Rev. B 57 1505 Google Scholar
[17]	Xiao R, Li H, Chen L 2012 Chem. Mater. 24 4242 Google Scholar
[18]	Jain A, Hautier G, Ong S P, Moore C J, Fischer C C, Persson K A, Ceder G 2011 Phys. Rev. B 84 045115 Google Scholar
[19]	Chen Y F, Jiang X, Li Y Y, Li P, Liu Q C, Fu G T, Xu L, Sun D M, Tang Y W 2018 Adv. Mater. Interfaces 5 1701015 Google Scholar
[20]	Zheng H F, Hu Z Y, Liu P F, Xu W J, Xie Q S, He W, Luo Q, Wang L S, Gu D D, Qu B H, Zhu Z Z, Peng D L 2020 Energy Storage Mater. 25 76 Google Scholar
[21]	Nakamura T, Ohta K, Hou X Y, Kimura Y, Tsuruta K, Tamenori Y, Aso R, Yoshida H, Amezawa K 2021 J. Mater. Chem. A 9 3657 Google Scholar
[22]	Limpijumnong S, Van de Walle C G 2004 Phys. Rev. B 69 035207 Google Scholar
[23]	Ouyang C Y, Šljivančanin Ž, Baldereschi A 2009 Phys. Rev. B 79 235410 Google Scholar
[24]	Reuter K, Scheffler M 2001 Phys. Rev. B 65 035406 Google Scholar
[25]	Hu W, Wang H W, Luo W W, Xu B, Ouyang C Y 2020 Solid State Ionics 347 115257 Google Scholar
[26]	Park J H, Lim J, Yoon J, K S, Gim J, Song J, Park H, Im D, Park M, Ahn D, Paik Y, Kim J 2012 Dalton Trans. 41 3053

Cited By

图 1 两种富锂锰基三元正极材料的结构对比　(a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂的晶体结构图; (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂的晶体结构图. 不同颜色的八面体分别表示: NiO₆灰色、CoO₆蓝色、MnO₆紫色. 氧为红色小球, 锂为绿色的球

Figure 1. Comparison of the structures for two Li-rich Mn-based ternary cathode materials. Crystal structures of (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂. The octahedra are denoted by different colors: NiO₆ gray, CoO₆ blue, and MnO₆ purple. Oxygen is given by red balls, lithium is shown by green balls.

DownLoad: Full-Size Img PowerPoint

图 2 两种三元材料中　(a) 双空位、三空位和四空位(V_2O, V_3O和V_4O)的形成能. 虚线表示同时拿掉n个氧的空位族形成能, 实线表示分别一个一个拿掉氧的空位族形成能; (b) 双空位、三空位和四空位平均到形成一个氧空位的形成能

Figure 2. Formation energies of oxygen of (a) bivacancy, trivacancy and quadruvacancy (V_2O, V_3O and V_4O) in two materials. The dashed line represents the vacancy formation energy of n oxygens detached at the same time, and the solid line represents the formation energy of oxygen detached one by one. (b) The formation energies of the double, triple and quadruple vacancy averaged to a single oxygen.

DownLoad: Full-Size Img PowerPoint

图 3 (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ 和 (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂材料中氧空位簇的形成能随温度的变化关系(氧分压为P = 0.2 bar (1 bar=1×10⁵ Pa)

Figure 3. Formation energy of oxygen vacancy clusters versus temperatures in (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ (oxygen partial pressure is P = 0.2 bar(1 bar=1×10⁵ Pa).

DownLoad: Full-Size Img PowerPoint

图 4 (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ 和 (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ 材料中氧空位簇的形成能随氧分压的变化关系(温度为T=300 K)

Figure 4. Formation energy of oxygen vacancy clusters versus oxygen partial pressure in (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ (temperature is T = 300 K).

DownLoad: Full-Size Img PowerPoint

图 5 (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ 和 (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ 材料中氧空位簇的形成能随氧分压的变化关系(温度为T=1000 K)

Figure 5. Formation energy of oxygen vacancy clusters versus oxygen partial pressure in (a) Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and (b) Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ (temperature is T = 1000 K).

DownLoad: Full-Size Img PowerPoint

图 6 两种材料中(a) V_nO-Li空位簇 (V_2-Li, V_3-Li 和V_4-Li) 的形成能以及(b) V_2-Li, V_3-Li 和V_4-Li 体系中平均到形成一个氧空位的形成能

Figure 6. Formation energies of (a) V_nO-Li clusters (i.e., V_2-Li, V_3-Li and V_4-Li) and (b) formation energy averaged to a single oxygen vacancy in two materials.

DownLoad: Full-Size Img PowerPoint

图 7 Li_1.2Ni_0.32Co_0.04Mn_0.44O₂材料中, V_2O-Li, V_3O-Li和V_4O-Li空位簇与替位点缺陷的相互作用能　(a) 过渡金属Ni或Mn被Mo替位; (b) 过渡金属Ni或Mn被Ti替位

Figure 7. Interaction energies between the V_2O-Li, V_3O-Li, V_4O-Li vacancy clusters and the substitutional defects in Li_1.2Ni_0.32Co_0.04Mn_0.44O₂: (a) Transition metal Ni or Mn substituted by Mo; (b) transition metal Ni or Mn substituted by Ti.

DownLoad: Full-Size Img PowerPoint

图 8 Li_1.167Ni_0.167Co_0.167Mn_0.5O₂材料中, V_2O-Li, V_3O-Li和V_4O-Li空位簇与替位点缺陷的相互作用能　(a) 过渡金属Ni或Mn被Mo替位; (b) 过渡金属Ni或Mn被Ti替位

Figure 8. Interaction energies between the V_2O-Li, V_3O-Li, V_4O-Li vacancy clusters and the substitutional defects in Li_1.167Ni_0.167Co_0.167Mn_0.5O₂: (a) Transition metal Ni or Mn substituted by Mo; (b) transition metal Ni or Mn substituted by Ti.

DownLoad: Full-Size Img PowerPoint

表 1 Li_1.2Ni_0.32Co_0.04Mn_0.44O₂和Li_1.167Ni_0.167Co_0.167Mn_0.5O₂三元材料中不等价单氧空位的形成能

Table 1. Formation energy of a single oxygen vacancy in Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ ternary materials.

单个氧空位的形成能 /eV

Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ Li_1.167Ni_0.167Co_0.167Mn_0.5O₂
V_O1 V_O2 V_O3 V_O4 V_O5 V_O6 V_O7 V_O8 V_O1 V_O2 V_O3 V_O4
2.0 3.31 2.17 4.43 4.15 3.03 2.86 4.27 2.3 2.80 3.12 3.20

DownLoad: CSV

表 2 Li_1.2Ni_0.32Co_0.04Mn_0.44O₂和Li_1.167Ni_0.167Co_0.167Mn_0.5O₂三元材料中氧空位族中的氧原子被一个一个分别脱去时的形成能

Table 2. Formation energy of an oxygen vacancy in vacancy clusters in Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ and Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ ternary materials, when the oxygen atoms are extracted one by one, respectively.

各个单氧空位的形成能 /eV

氧空位的序号(第n个氧) 1 2 3 4
Li_1.2Ni_0.32Co_0.04Mn_0.44O₂ 2.00 2.78 1.70 1.14
Li_1.167Ni_0.167Co_0.167Mn_0.5O₂ 2.80 3.17 3.02 2.40

DownLoad: CSV

[1]	Dunn B, Kamath H, Tarascon J M 2011 Science 334 928 Google Scholar
[2]	Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D 2011 Energy Environ. Sci. 4 3243 Google Scholar
[3]	Nitta N, Wu F, Lee J T, Yushin G 2015 Mater. Today 18 252 Google Scholar
[4]	Yuan L X, Wang Z H, Zhang W X, Hu X L, Chen J T, Huang Y H, Goodenough J B 2011 Energy Environ. Sci. 4 269 Google Scholar
[5]	Liu J L, Hou M Y, Yi J, Guo S S, Wang C X, Xia Y Y 2014 Energy Environ. Sci. 7 705 Google Scholar
[6]	Csernica P M, Kalirai S S, Gent W E, Lim K, Yu Y S, Liu Y, Ahn S J, Kaeli E, Xu X, Stone K H, Marshall A F, Sinclair R, Shapiro D A, Toney M F, Chueh W C 2021 Nat. Energy 6 642 Google Scholar
[7]	Hu E Y, Yu X Q, Lin R Q, Bi X X, Lu J, Bak S M, Nam K W, Xin H L, Jaye C, Fischer D A, Amine K, Yang X Q 2018 Nat. Energy 3 690 Google Scholar
[8]	Zhu Z, Yu D W, Yang Y, Su C, Huang Y M, Dong Y H, Waluyo I, Wang B M, Hunt A, Yao X H, Lee J, Xue W J, Li J 2019 Nat. Energy 4 1049 Google Scholar
[9]	Yan P, Zheng J, Tang Z K, Devaraj A, Chen G, Amine K, Zhang J G, Liu L M, Wang C 2019 Nat. Nanotechnol. 14 602 Google Scholar
[10]	Lee E, Persson K A 2014 Adv. Energy Mater. 4 1400498 Google Scholar
[11]	Hoang K 2015 Phys. Rev. Appl. 3 024013 Google Scholar
[12]	史晓红, 陈京金, 曹昕睿, 吴顺情, 朱梓忠 2022 物理学报 71 178202 Google Scholar Shi X H, Chen J J, Cao X R, Wu S Q, Zhu ZZ 2022 Acta Phy. Sin. 71 178202 Google Scholar
[13]	Michaud-Rioux V, Zhang L, Guo H 2016 J. Comput. Phys. 307 593 Google Scholar
[14]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[15]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[16]	Dudarev S L, Botton G A, Savrasov S Y, Humphreys C J, Sutton A P 1998 Phys. Rev. B 57 1505 Google Scholar
[17]	Xiao R, Li H, Chen L 2012 Chem. Mater. 24 4242 Google Scholar
[18]	Jain A, Hautier G, Ong S P, Moore C J, Fischer C C, Persson K A, Ceder G 2011 Phys. Rev. B 84 045115 Google Scholar
[19]	Chen Y F, Jiang X, Li Y Y, Li P, Liu Q C, Fu G T, Xu L, Sun D M, Tang Y W 2018 Adv. Mater. Interfaces 5 1701015 Google Scholar
[20]	Zheng H F, Hu Z Y, Liu P F, Xu W J, Xie Q S, He W, Luo Q, Wang L S, Gu D D, Qu B H, Zhu Z Z, Peng D L 2020 Energy Storage Mater. 25 76 Google Scholar
[21]	Nakamura T, Ohta K, Hou X Y, Kimura Y, Tsuruta K, Tamenori Y, Aso R, Yoshida H, Amezawa K 2021 J. Mater. Chem. A 9 3657 Google Scholar
[22]	Limpijumnong S, Van de Walle C G 2004 Phys. Rev. B 69 035207 Google Scholar
[23]	Ouyang C Y, Šljivančanin Ž, Baldereschi A 2009 Phys. Rev. B 79 235410 Google Scholar
[24]	Reuter K, Scheffler M 2001 Phys. Rev. B 65 035406 Google Scholar
[25]	Hu W, Wang H W, Luo W W, Xu B, Ouyang C Y 2020 Solid State Ionics 347 115257 Google Scholar
[26]	Park J H, Lim J, Yoon J, K S, Gim J, Song J, Park H, Im D, Park M, Ahn D, Paik Y, Kim J 2012 Dalton Trans. 41 3053

[1]	Zhong Jian-Cheng, Zhang Xiao-Tian, Lin Chang-Qing, Xue Yang, Tang Huan, Huang Dan. Top cell design and optimization of all-chalcopyrite CuGaSe₂/CuInSe₂ two-terminal tandem solar cells: first-principles calculations and device simulations. Acta Physica Sinica, 2024, 0(0): 0-0. doi: 10.7498/aps.73.20240187
[2]	Yang Hai-Lin, Chen Qi-Li, Gu Xing, Lin Ning. First-principles calculations of O-atom diffusion on fluorinated graphene. Acta Physica Sinica, 2023, 72(1): 016801. doi: 10.7498/aps.72.20221630
[3]	Shi Xiao-Hong, Chen Jing-Jin, Cao Xin-Rui, Wu Shun-Qing, Zhu Zi-Zhong. Formation of oxygen vacancies in Li-rich Mn-based cathode material Li_1.167Ni_0.167Co_0.167Mn_0.5O₂. Acta Physica Sinica, 2022, 71(17): 178202. doi: 10.7498/aps.71.20220274
[4]	Liu Zi-Yuan, Pan Jin-Bo, Zhang Yu-Yang, Du Shi-Xuan. First principles calculation of two-dimensional materials at an atomic scale. Acta Physica Sinica, 2021, 70(2): 027301. doi: 10.7498/aps.70.20201636
[5]	Wang Yan, Chen Nan-Di, Yang Chen, Zeng Zhao-Yi, Hu Cui-E, Chen Xiang-Rong. Thermoelectric transport properties of two-dimensional materials XTe₂ (X = Pd, Pt) via first-principles calculations. Acta Physica Sinica, 2021, 70(11): 116301. doi: 10.7498/aps.70.20201939
[6]	Luan Li-Jun, He Yi, Wang Tao, Liu Zong-Wen. First-principles study of e interface interaction and photoelectric properties of the solar cell heterojunction CdS/CdMnTe. Acta Physica Sinica, 2021, 70(16): 166302. doi: 10.7498/aps.70.20210268
[7]	Lin Hong-Bin, Lin Chun, Chen Yue, Zhong Ke-Hua, Zhang Jian-Min, Xu Gui-Gui, Huang Zhi-Gao. First-principles study of effect of Mg doping on structural stability and electronic structure of LiCoO₂ cathode material. Acta Physica Sinica, 2021, 70(13): 138201. doi: 10.7498/aps.70.20210064
[8]	Huang Wen-Jun, Wang Ya-Ping, Cao Xin-Rui, Wu Shun-Qing, Zhu Zi-Zhong. Electronic structures and defect properties of lithium-rich manganese-based ternary material Li_1.208Ni_0.333Co_0.042Mn_0.417O₂. Acta Physica Sinica, 2021, 70(20): 208201. doi: 10.7498/aps.70.20210398
[9]	Hu Qian-Ku, Qin Shuang-Hong, Wu Qing-Hua, Li Dan-Dan, Zhang Bin, Yuan Wen-Feng, Wang Li-Bo, Zhou Ai-Guo. First-principles calculations of stabilities and physical properties of ternary niobium borocarbides and tantalum borocarbides. Acta Physica Sinica, 2020, 69(11): 116201. doi: 10.7498/aps.69.20200234
[10]	Yin Yuan, Li Ling, Yin Wan-Jian. Theoretical and computational study on defects of solar cell materials. Acta Physica Sinica, 2020, 69(17): 177101. doi: 10.7498/aps.69.20200656
[11]	Zheng Lu-Min, Zhong Shu-Ying, Xu Bo, Ouyang Chu-Ying. First-principles study of rare-earth-doped cathode materials Li₂MnO₃ in Li-ion batteries. Acta Physica Sinica, 2019, 68(13): 138201. doi: 10.7498/aps.68.20190509
[12]	Chen Dong-Yun, Gao Ming, Li Yong-Hua, Xu Fei, Zhao Lei, Ma Zhong-Quan. First principle study of formation mechanism of molybdenum-doped amorphous silica in MoO₃/Si interface. Acta Physica Sinica, 2019, 68(10): 103101. doi: 10.7498/aps.68.20190067
[13]	Mo Man, Zeng Ji-Shu, He Hao, Zhang Liang, Du Long, Fang Zhi-Jie. The first-principle study on the formation energies of Be, Mg and Mn doped CuInO₂. Acta Physica Sinica, 2019, 68(10): 106102. doi: 10.7498/aps.68.20182255
[14]	Huang Bing-Quan, Zhou Tie-Ge, Wu Dao-Xiong, Zhang Zhao-Fu, Li Bai-Kui. Properties of vacancies and N-doping in monolayer g-ZnO: First-principles calculation and molecular orbital theory analysis. Acta Physica Sinica, 2019, 68(24): 246301. doi: 10.7498/aps.68.20191258
[15]	Luo Ming-Hai, Li Ming-Kai, Zhu Jia-Kun, Huang Zhong-Bing, Yang Hui, He Yun-Bin. First-principles study on thermodynamic properties of CdxZn1-xO alloys. Acta Physica Sinica, 2016, 65(15): 157303. doi: 10.7498/aps.65.157303
[16]	Hao Hong-Fei, Wang Jing, Sun Feng, Zhang Lan-Ting. First-principles calculation of preferential site occupation of Dy ions in Nd2Fe14B lattice and its effect on local magnetic moments of Fe ions. Acta Physica Sinica, 2013, 62(11): 117501. doi: 10.7498/aps.62.117501
[17]	Zhang Zhao-Fu, Zhou Tie-Ge, Zuo Xu. First-principles calculations of h-BN monolayers by doping with oxygen and sulfur. Acta Physica Sinica, 2013, 62(8): 083102. doi: 10.7498/aps.62.083102
[18]	Liu Xian-Kun, Liu Ying, Qian Da-Zhi, Zheng Zhou. First-principles study of helium atom doped interstitial sites of Al. Acta Physica Sinica, 2010, 59(9): 6450-6456. doi: 10.7498/aps.59.6450
[19]	Hou Qing-Yu, Zhang Yue, Chen Yue, Shang Jia-Xiang, Gu Jing-Hua. Effects of the concentration of oxygen vacancy of anatase on electric conducting performance studied by frist principles calculations. Acta Physica Sinica, 2008, 57(1): 438-442. doi: 10.7498/aps.57.438
[20]	Ye Hong-Gang, Chen Guang-De, Zhu You-Zhang, Zhang Jun-Wu. First principle study of the native defects in hexagonal aluminum nitride. Acta Physica Sinica, 2007, 56(9): 5376-5381. doi: 10.7498/aps.56.5376

Catalog

Vol. 72, Issue 7 - 2023-04-05

Metrics

Abstract views: 3416
PDF Downloads: 118
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板