在鋰離子電池充放電過程中，電解質為電池重要組成，用以在電池內部傳輸鋰離子。眾多電解質種類中，膠態電解質在室溫下具有高導電性並且高安全性。在此我們結合分子模擬(AA-MD) 和耗散粒子動力學模擬(DPD) 來探討混摻奈米添加劑對於丙烯腈-乙酸乙烯酯共聚物(PAN-co-PVAc，PAV) 和聚甲基丙烯酸甲酯(PMMA)共混成的膠態電解質之鋰離子傳輸機制。我們探討了三種奈米添加劑，包括氧化石墨烯量子點(GOQD)、二氧化鈦(TiO2)、二氧化矽(SiO2)，其表面上的離子親和力，並進一步分析高分子鏈段和奈米添加劑周圍的鋰離子動力學性質。我們也利用DPD 模擬研究奈米添加劑對高分子自組裝結構形態變化的影響。
全原子模擬結果顯示若將PMMA 共混到PAV 中會略微降低高分子薄膜表面的陰離子親和力。但PMMA 在電解質中會包裹在高分子纖維內，高分子聚合物膜表面上的陰離子親和力降低效果是有限的。在三種奈米添加劑中，TiO2 與陰離子具有最強的親和力，導致降低陰離子擴散係數，但可提升鋰離子在奈米粒子表面上的擴散係數。透過離子-溶劑配位的最小化可使更多的自由鋰離子平順地傳輸於TiO2 表面。GOQD 可區分為富含醚基和富含羥基表面。由於其兩個不同表面上的相反介面電位，使得GOQD 具有中度陰離子親和力。此外GOQD 可有效抑制表面離子-溶劑配位的形成，增加更多的自由鋰離子。SiO2 則具有最弱的陰離子親和力，故其表面的PF6 擴散係數最高。雖然SiO2 也具有表面離子-溶劑配位的抑制作用，但其缺乏固定陰離子的能力，抵銷自由鋰離子增加效應。DPD 模擬結果顯示PMMA 會橋接在PAV 上的VAc，故在電解液中可良好地分散並包裹在高分子纖維內。而奈米添加劑與PMMA 具有良好的交互作用，使奈米粒子可平均分佈於纖維表面並與電解液接觸。PMMA 的添加會導致高分子纖維孔道半徑的些微減小。由於對整個高分子構型的抑制作用，摻雜有奈米粒子的膠態電解質的孔道顯著小於傳統膠態電解質，並提升高分子網路與電解質之接觸。
最後，我們總結了高分子纖維，奈米添加劑和離子之間的競爭關係。路易斯酸型奈米粒子可附著在高分子聚合物上並且與陰離子具有更強的相互作用以促進鋰離子傳導。然而，路易斯鹼型奈米粒子則與高分子聚合物競爭與鋰離子之間的相互作用，導致減緩鋰離子傳導。在奈米尺度上，奈米粒子可以固定陰離子並降低表面的離子-溶劑配位。在介觀尺度上，奈米粒子會附著在分散良好的PMMA 上並暴露於電解質中，並且減少高分子纖維孔道半徑。本模擬結果可與實驗數據相互應並進一步提供奈米添加劑對膠態電解質鋰離子傳輸的分子機制。
關鍵字: 鋰離子電池、膠態電解質、奈米粒子、多尺度分子模擬

Electrolyte is an important component of lithium ion battery (LIB) that transporting Li+ within LIB during charging/ discharging process. Among various categories of electrolytes, gel polymer electrolytes (GPEs) have the advantage of high conductivity at room temperature and high safety. Here, we combined all-atom molecular dynamics (AA-MD) and dissipative particle dynamics (DPD) simulation to examine the mechanism of nanoparticle on affecting Li+ transport within the GPE composed of poly (acrylonitrile-co-vinyl acetate) (PAV) blended with poly (methyl methacrylate) (PMMA). In particular, we investigated the ion affinity on surface of three types of nanofillers, including graphene oxide quantum dot (GOQD), Titanium dioxide (TiO2), and Silicon dioxide (SiO2). We examined the dynamic properties of lithium ions near the polymer segments and nanoparticles with AA-MD. Furthermore, we utilized DPD simulation to study the morphology variations of self-assembled polymer framework with the addition of nanoparticles.
AA-MD simulation results showed that blending PMMA into PAV slightly decreases the anion affinity PF6 on the surface of polymer film. Yet, the fact of PMMA wrapped inside the polymer framework while soaked in electrolytes only leads to a minor effect on PF6 affinity near the polymer film. Among three nanofillers, TiO2 nanoparticle exhibits the strongest affinity with PF6 , resulting in the lowest diffusion coefficient of PF6 and the highest diffusion coefficient of Li+. Also, the minimized coordination within the Li+ solvation shell allows more free-Li+ to transfer smoothly on TiO2 surface. GOQD has two different surfaces, i.e. a rich -O- one and a rich -OH one, respectively. This attributes a medium affinity to PF6 due to the opposite electrostatic potentials on two surfaces. In addition, GOQD suppresses the formation of ion-solvent clusters with less amount of Li+-DEC coordination near the surface, increasing the amount of free Li+. SiO2 exhibits the highest PF6 diffusion coefficient near its surface due to the weakest affinity with PF6 . The suppressive effect on coordination of ion solvent (Li+-EC) also occurs on the SiO2 surface. Yet SiO2 lacks the ability of immobilizing PF6 , offsetting the free Li+ transport. DPD simulation results showed that PMMA segments attach and bridge on PVAc functional group of PAV chains, thereby being well-dispersed and wrapped inside the polymer framework while soaked in electrolytes. Nanofiller with strong interaction with PMMA is then well-dispersed on the polymer framework surface and exposed to electrolyte. The addition of PVAc reduce the electrolyte channel size within the framework. The channel size of GPEs doped with nanofillers are significantly smaller than that of ordinary GPEs due to the suppressive effect on whole polymer morphology, enhancing the contact between polymer framework and electrolyte.
Conclusively, we summarized a competitive relationship among polymer fibers, nanofillers and ions. A Lewis acid-type nanoparticle attaches on polymer PAVM and has stronger interaction with PF6 to facilitate the Li+ conduction. However, a Lewis base-type nanoparticle competes with polymer PAVM for the interaction between Li+, causing the decreasing Li+ conduction mechanism. At nanoscale, nanoparticles can immobilize the anion and minimize the coordination of ion-solvent near the surface. At mesoscale, nanoparticles attach on welldispersed PMMA, distribute on polymer framework surface, and decrease the electrolyte channel size. This enhances the microscopic effects described above. The presented results provide molecular insights for GPE doped with nanofillers that correspond to the experimental observation.
Keywords: lithium ion battery, gel polymer electrolyte, nanoparticle, multiscale molecular
simulation

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