Dimethyl methylphosphonate-based nonflammable electrolyte and high safety lithium-ion batteries

Dimethyl methylphosphonate (DMMP) was used as a cosolvent to reformulate the nonflammable electrolyte of 1 M LiPF₆/EC + DEC + DMMP (1:1:2 wt.) in order to improve the safety characteristics of lithium-ion batteries. The flammability, cell performance, low-temperature performance and thermal stability of the DMMP-based electrolyte were compared with the electrolyte of 1 M LiPF₆/EC + DEC (1:1 wt.). The nonflammable electrolyte exhibits good oxidation stability at the LiCoO₂ cathode and poor reduction stability at the mesocarbon microbead (MCMB) and surface-modified graphite (SMG) anodes. The addition of vinyl ethylene carbonate (VEC) to the DMMP-based electrolyte provided a significant improvement in the reduction stability at the carbonaceous electrodes. Furthermore, it was found that the addition of DMMP resulted in optimized low-temperature performance and varied thermal stability of the electrolytes. All of the results indicated the novel DMMP-based electrolyte is a promising nonflammable electrolyte to resolve the safety concerns of lithium-ion batteries.     

Dimethyl methylphosphonate (DMMP) as an efficient flame retardant additive for the lithium-ion battery electrolytes

Dimethyl methylphosphonate (DMMP) was used as a flame retardant additive to 1 M LiPF₆/EC + DEC system. The flammability, electrochemical stability and cycling performance of electrolyte containing DMMP were studied. The addition of DMMP to electrolytes provides a significant suppression in the flammability of the electrolyte concluded from the measurements of self-extinguish time and limited oxygen index. The totally nonflammable electrolytes can be achieved with only 10 wt.% DMMP addition—the highly efficient retardant additive. The addition of DMMP causes little damage on the cell electrochemical performance. DMMP is a promising flame retardant additive to improve the safety of lithium-ion batteries.     

Possible use of non-flammable phosphonate ethers as pure electrolyte solvent for lithium batteries

Dimethyl methyl phosphonate (DMMP) was selected and tested as a non-flammable solvent for primary and secondary lithium batteries, because of its non-flammability, good solvency of lithium salts and appropriate liquidus properties. Experimental results demonstrated that DMMP can solvate considerable amount of commonly used lithium salts to form non-flammable and Li⁺-conducting electrolyte, which has very wide electrochemical window (>5 V vs. Li) and excellent electrochemical compatibility with metallic lithium anode and oxide cathodes. Primary Li–MnO₂ cells using DMMP-based electrolyte showed almost the same discharge performances as those using organic carbonate electrolytes, and also, Li–LiMn₂O₄ cells using DMMP electrolyte exhibited greatly improved cycleability and dischargeability, suggesting a feasible application of this new electrolyte for constructing high performance and non-flammable lithium batteries.     

Nonflammable electrolyte for 3-V lithium-ion battery with spinel materials LiNi0.5Mn1.5O4 and Li4Ti5O12

The compatibility between dimethyl methylphosphonate (DMMP)-based electrolyte of 1 M LiPF₆/EC + DMC + DMMP (1:1:2 wt.) and spinel materials Li₄Ti₅O₁₂ and LiNi_0.5Mn_1.5O₄ was reviewed, respectively. The cell performance and impedance of 3-V LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ lithium-ion cell with the DMMP-based nonflammable electrolyte was compared with the baseline electrolyte of 1 M LiPF₆/EC + DMC (1:1 wt.). The nonflammable DMMP-based electrolyte exhibited good compatibility with spinel Li₄Ti₅O₁₂ anode and high-voltage LiNi_0.5Mn_1.5O₄ cathode, and acceptable cycling performance in the LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ full-cell, except for the higher impedance than that in the baseline electrolyte. All of the results disclosed that the 3 V LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ lithium-ion battery was a promising choice for the nonflammable DMMP-based electrolyte.     

A new phosphate-based nonflammable electrolyte solvent for Li-ion batteries

A new fire-retardant—dimethyl(2-methoxyethoxy)methylphosphonate (DMMEMP) has been synthesized and evaluated as a high safe electrolyte solvent for lithium-ion batteries. This report summarizes the physical and electrochemical properties of the new compound. It is found that, this nonflammable phosphonate has a moderate viscosity, a high dielectric constant and a good thermal stability. It can provide a wide electrochemical stability window of 0–5.5 V (vs. Li⁺/Li), a high conductivity of 2.0 mS cm⁻¹ at 20 °C with 1 M LiTFSI. The electrochemical performance investigated with the Li/LiFePO₄ half-cells shows a good capacity of 148.1 mAh g⁻¹ and a coulombic efficiency close to 100% at the 10th cycle.     

New electrolytes based on glutaronitrile for high energy/power Li-ion batteries

Glutaronitrile, CN[CH₂]₃CN, is evaluated as a co-solvent in thermally and (anodically) electrochemically stable electrolyte mixtures suitable for high energy/power Li-ion batteries. Linear sweep voltammetry scans indicate an electrochemical anodic stability of more than 6 V versus Li⁺/Li for the 1 M LiTFSI electrolytes. Glutaronitrile and its ethylene carbonate electrolyte solutions show high ionic conductivities and low viscosities reaching 5 mS cm⁻¹ and 7 cP, respectively, at 20 °C. Aluminum corrosion tests of the solutions showed an improved protective resistance up to 4.4 V. Lithium ion batteries incorporating graphite as an anode and LiCoO₂ as the cathode material were assembled using a glutaronitrile electrolyte mixture, whose stability on graphite was greatly enhanced by the use of ethylene carbonate as a co-solvent and Li (bioxalatoborate) (LiBOB) as a co-salt, and these cells showed moderately good discharge capacities with low capacity fade up to the 100th cycle.     

Effects of Lewis-acid polymer on the electrochemical properties of alkylphosphate-based non-flammable gel electrolyte

Non-flammable polymer gel electrolytes (NPGE) consisting of 1.0 mol dm⁻³ (=M) LiBF₄/EC + DEC + TEP (55:25:20 volume ratio) + PVdF-HFP (EC: ethylene carbonate, DEC: diethyl carbonate, TEP: triethylphosphate, PVdF-HFP: poly(vinyledenefluoride-co-hexafluoropropylene)) have been developed for rechargeable lithium batteries. The effects of addition of Lewis-acid polymer (LAP) with different mole ratio in NPGE have been studied. The addition of LAP improved physico-chemical properties of NPGE, viz ionic conductivity and lithium ion transport number, as well as mechanical and thermal properties. The ionic conductivity of the gel electrolyte containing LAP reached that of the base solution electrolyte (1.0 M LiBF₄/EC + DEC + TEP (55:25:20)) along with better mechanical properties. Interfacial resistance at Li-metal electrode/NPGE was also improved by introducing LAP in the gel.     

A novel high-performance gel polymer electrolyte membrane basing on electrospinning technique for lithium rechargeable batteries

Nonwoven films of composites of thermoplastic polyurethane (TPU) with different proportion of poly(vinylidene fluoride) (PVdF) (80, 50 and 20%, w/w) are prepared by electrospinning 9 wt% polymer solution at room temperature. Then the gel polymer electrolytes (GPEs) are prepared by soaking the electrospun TPU-PVdF blending membranes in 1 M LiClO₄/ethylene carbonate (EC)/propylene carbonate (PC) for 1 h. The gel polymer electrolyte (GPE) shows a maximum ionic conductivity of 3.2 × 10⁻³ S cm⁻¹ at room temperature and electrochemical stability up to 5.0 V versus Li⁺/Li for the 50:50 blend ratio of TPU:PVdF system. At the first cycle, it shows a first charge-discharge capacity of 168.9 mAh g⁻¹ when the gel polymer electrolyte (GPE) is evaluated in a Li/PE/lithium iron phosphate (LiFePO₄) cell at 0.1 C-rate at 25 °C. TPU-PVdF (50:50, w/w) based gel polymer electrolyte is observed much more suitable than the composite films with other ratios for high-performance lithium rechargeable batteries.     

Gel polymer electrolyte lithium-ion cells with improved low temperature performance

For a number of NASA's future planetary and terrestrial applications, high energy density rechargeable lithium batteries that can operate at very low temperature are desired. In the pursuit of developing Li-ion batteries with improved low temperature performance, we have also focused on assessing the viability of using gel polymer systems, due to their desirable form factor and enhanced safety characteristics. In the present study we have evaluated three classes of promising liquid low-temperature electrolytes that have been impregnated into gel polymer electrolyte carbon-LiMn₂O₄-based Li-ion cells (manufactured by LG Chem. Inc.), consisting of: (a) binary EC + EMC mixtures with very low EC-content (10%), (b) quaternary carbonate mixtures with low EC-content (16–20%), and (c) ternary electrolytes with very low EC-content (10%) and high proportions of ester co-solvents (i.e., 80%). These electrolytes have been compared with a baseline formulation (i.e., 1.0 M LiPF₆ in EC + DEC + DMC (1:1:1%, v/v/v), where EC, ethylene carbonate, DEC, diethyl carbonate, and DMC, dimethyl carbonate). We have performed a number of characterization tests on these cells, including: determining the rate capacity as a function of temperature (with preceding charge at room temperature and also at low temperature), the cycle life performance (both 100% DOD and 30% DOD low earth orbit cycling), the pulse capability, and the impedance characteristics at different temperatures. We have obtained excellent performance at low temperatures with ester-based electrolytes, including the demonstration of >80% of the room temperature capacity at −60 °C using a C/20 discharge rate with cells containing 1.0 M LiPF₆ in EC + EMC + MB (1:1:8%, v/v/v) (MB, methyl butyrate) and 1.0 M LiPF₆ in EC + EMC + EB (1:1:8%, v/v/v) (EB, ethyl butyrate) electrolytes. In addition, cells containing the ester-based electrolytes were observed to support 5C pulses at −40 °C, while still maintaining a voltage >2.5 V at 100 and 80% state-of-charge (SOC).     

Electrochemical performance of nonflammable polymeric gel electrolyte containing triethylphosphate

Nonflammable polymeric gel electrolyte has been prepared by immobilizing 1 M LiBF₄/EC + DEC + TEP (55:25:20, v/v/v, EC: ethylene carbonate, DEC: diethyl carbonate and TEP: triethylphosphate) solution in poly(vinylidene fluoride-co-hexafluoro propylene) (PVdF-HFP) where TEP acts as a fire-retardant solvent in the gel electrolyte. The polymeric gel electrolyte has a high value of ionic conductivity of 1.76 mS cm⁻¹ at 28 °C. Thermal safety calorimetry (TSC) experiments show good thermal stability of the gel electrolyte. Cyclic voltammetry and charge/discharge cycling tests were performed on LiMn₂O₄/gel electrolyte and graphite/gel electrolyte half cells. The gel electrolyte works well for graphite/LiMn₂O₄ cell although some improvement in the cycleability of the graphite electrode is still needed.     

New electrolytes for lithium ion batteries using LiF salt and boron based anion receptors

The thermal and electrochemical stability, as well as compatibility with various bench mark cathode and anode materials of two new lithium fluoride salt (LiF) based electrolytes have been studied. These two new electrolytes are formed by using boron-based anion receptors, tris(pentafluorophenyl) borane (TPFPB), or tris(2H-hexafluoroisopropyl) borate (THFPB) as additives, which were designed and synthesized at Brookhaven National Laboratory (BNL), to dissolve the LiF salt in carbonate solvents. The transference number of Li⁺ for these electrolytes is as high as 0.7 and the room-temperature conductivity is around 2 × 10⁻³ S cm⁻¹. The electrolytes containing propylene carbonate (PC) show superior low-temperature conductivity properties. The electrochemical window is approaching 5.0 V. It was also found that the new electrolytes work well with LiCoO₂ or LiMn₂O₄ cathodes. However, when PC containing electrolytes were used, PC co-intercalation is still a problem for graphite anodes. The formation of a stable solid electrolyte interface layer on the surface of anode in this type of electrolyte needs to be studied further.     

Functional interface of polymer modified graphite anode

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm⁻³ LiClO₄ ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li⁺, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge–discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.     

Improved electrolytes for Li-ion batteries: Mixtures of ionic liquid and organic electrolyte with enhanced safety and electrochemical performance

Physical and electrochemical characteristics of Li-ion battery systems based on LiFePO₄ cathodes and graphite anodes with mixture electrolytes were investigated. The mixed electrolytes are based on an ionic liquid (IL), and organic solvents used in commercial batteries. We investigated a range of compositions to determine an optimum conductivity and non-flammability of the mixed electrolyte. This led us to examine mixtures of ILs with the organic electrolyte usually employed in commercial Li-ion batteries, i.e., ethylene carbonate (EC) and diethylene carbonate (DEC). The IL electrolyte consisted of (trifluoromethyl sulfonylimide) (TFSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) as the cation. The physical and electrochemical properties of some of these mixtures showed an improvement characteristics compared to the constituents alone. The safety was improved with electrolyte mixtures; when IL content in the mixture is ≥40%, no flammability is observed. A stable SEI layer was obtained on the MCMB graphite anode in these mixed electrolytes, which is not obtained with IL containing the TFSI-anion. The high-rate capability of LiFePO₄ is similar in the organic electrolyte and the mixture with a composition of 1:1. The interface resistance of the LiFePO₄ cathode is stabilized when the IL is added to the electrolyte. A reversible capacity of 155 mAh g⁻¹ at C/12 is obtained with cells having at least some organic electrolyte compared to only 124 mAh g⁻¹ with pure IL. With increasing discharge rate, the capacity is maintained close to that in the organic solvent up to 2 C rate. At higher rates, the results with mixture electrolytes start to deviate from the pure organic electrolyte cell. The evaluation of the Li-ion cells; LiFePO₄//Li₄Ti₅O₁₂ with organic and, 40% mixture electrolytes showed good 1st CE at 98.7 and 93.0%, respectively. The power performance of both cell configurations is comparable up to 2 C rate. This study indicates that safety and electrochemical performance of the Li-ion battery can be improved by using mixed IL and organic solvents.     

Fused ring and linking groups effect on overcharge protection for lithium-ion batteries

The derivatives of 1,3-benzodioxan (DBBD1) and 1,4-benzodioxan (DBBD2) bearing two tert-butyl groups have been synthesized as new redox shuttle additives for overcharge protection of lithium-ion batteries. Both compounds exhibit a reversible redox wave over 4 V vs Li/Li⁺ with better solubility in a commercial electrolyte (1.2 M LiPF₆ dissolved in ethylene carbonate/ethyl methyl carbonate (EC/EMC 3/7) than the di-tert-butyl-substituted 1,4-dimethoxybenzene (DDB). The electrochemical stability of DBBD1 and DBBD2 was tested under charge/discharge cycles with 100% overcharge at each cycle in MCMB/LiFePO₄ and Li₄Ti₅O₁₂/LiFePO₄ cells. DBBD2 shows significantly better performance than DBBD1 for both cell chemistries. The structural difference and reaction energies for decomposition have been studied by density functional calculations.     

A new lithium salt with dihydroxybenzene and lithium tetrafluoroborate for lithium battery electrolytes

A new unsymmetrical lithium salt containing F⁻, C₆H₄O₂²⁻ [dianion of 1,2-benzenediol], lithium difluoro(1,2-benzene-diolato(2-)-o,o′)borate (LDFBDB) is synthesized and characterized. Its thermal decomposition in nitrogen begins at 170 °C. The cyclic voltammetry study shows that the LDFBDB solution in propylene carbonate (PC) is stable up to 3.7 V versus Li⁺/Li. It is soluble in common organic solvents. The ionic dissociation properties of LDFBDB are examined by conductivity measurements in PC, PC+ ethyl methyl carbonate (EMC), PC + dimethyl ether (DME), PC + ethylene carbonate (EC) + EMC solutions. The conductivity values of the 0.564 mol dm⁻³ LDFBDB electrolyte in PC + DME solution is 3.90 mS cm⁻¹. All these properties of the new lithium salt including the thermal characteristics, electrochemical stabilities, solubilities, ionic dissociation properties are studied and compared with those of its derivatives, lithium difluoro(3-fluoro-1,2-benzene-diolato(2-)-o,o′)borate (FLDFBDB), lithium [3-fluoro-1,2-benzenediolato(2-)-o,o′ oxalato]borate (FLBDOB), and lithium bis(oxalate)borate (LBOB).     

Improvement of cyclability of Si as anode for Li-ion batteries

Silicon working as anode for Li-ion batteries has attracted much attention due to its high capacity (∼4200 mAh g⁻¹). However, due to the large volume expansion during lithiation, the capacity of silicon fades very fast. In this systematic study, we focus on the issue to fight the capacity fading. Results show that Si with sodium carboxymethyl cellulose (Na-CMC) as a polymer binder exhibits a better cyclability than that with poly(vinylidene fluoride) (PVDF). Yet differing from the system used in PVDF, the addition of vinylene carbonate (VC) does not improve or even worsens the performance of the system using Na-CMC. In addition, the small particle size of Si, a large amount of carbon black (CB), the good choice of electrolyte/conducting salt and charge-discharge window also play important roles to enhance the cyclability of Si. It is found that electrode consisting of 40 wt.% nano-Si, 40 wt.% carbon black and 20 wt.% Na-CMC (pH 3.5) displays the best cyclability, and in the voltage range from 0 to 0.8 V, after 200 cycles, its capacity can still keep 738 mAh g⁻¹ (C/2, in 1 M LiPF₆ ethylene carbonate/diethyl carbonate electrolyte, with VC-free), almost twice as that of graphite.     

Macroporous nanocomposite polymer electrolyte for lithium-ion batteries

A novel macroporous nanocomposite polymer membrane (NCPM) based on poly(vinylidene difluoride-co-hexafluoropropylene) [P(VDF-HFP)] copolymer was prepared by in situ hydrolysis of Ti(OC₄H₉)₄ using a non-solvent-induced phase separation technique. SEM micrograph shows that the yielding TiO₂ nanoparticles are dispersed uniformly in the polymer matrix and there are a lot of spherical macropores connecting with each other by some smaller pores. DSC results exhibit that the crystallinity of polymer matrix decreases with the incorporation of TiO₂ nanoparticles. The tensile stress of the NCPM is 9.69 MPa and its fracture strain 74.4%. After immersion in 1.0 mol l⁻¹ LiPF₆/ethyl carbonate (EC)–dimethyl carbonate (DMC), the ionic conductivity of the obtained nanocomposite polymer electrolyte (NCPE) is 0.98 × 10⁻³ S cm⁻¹ at 20 °C. Lithium-ion batteries, which use this kind of NCPE as the separator and electrolyte, display good discharging performance at different current densities, presenting promise for its practical application.     

Properties of the lithium and graphite-lithium anodes in N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide

The ternary [Li⁺]_0.09[MePrPyr⁺]_0.41[NTf₂⁻]_0.50 room temperature ionic liquid was obtained by dissolution of solid lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂) in liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([MePrPyr⁺][NTf₂⁻]), and studied as an electrolyte for lithium-ion batteries. The graphite-lithium (C₆Li) anode, working together with vinylene carbonate as an additive showed ca. 90% of its initial discharge capacity after 50 cycles. The addition of vinylene carbonate to the neat ionic liquid results in the formation of the protective coating (SEI) on both the lithium and graphite anodes. The SEI formation increases the rate of the charge transfer reaction as well as protects the anode from chemical passivation (corrosion). The graphite-lithium (C₆Li) anode shows good cyclability and Coulombic efficiency in the presence of 10 wt.% of vinylene carbonate as an additive to the ionic liquid.     

2,2-Dimethoxy-propane as electrolyte additive for lithium-ion batteries

2,2-Dimethoxy-propane (DMP) was studied as an additive in 1 mol dm⁻³ LiPF₆ ethylene carbonate and diethyl carbonate (1:1, w/w) for lithium-ion battery, which was characterized by cyclic voltammetry and half cell tests. Cyclic voltammetry and half cell data show that the use of DMP as an additive to the organic solutions at very low level (ca. 0.005 wt%) offers the advantage of forming fully developed passive films on the graphite anode surface. The electrochemical performance of the additive-containing electrolytes in combination with LiCoO₂ cathode and graphitic anode was also tested in commercial cells 103448. The results reveal that the cyclic life test and storage performance at high temperature (ca. 60 °C) in electrolyte with DMP additive was better than that in an electrolyte without additive. Therefore, DMP can be considered as a desirable additive in electrolyte for lithium-ion batteries operating at high temperature, ca. 60 °C.     

Electrochromic devices employing methacrylate-based polymer electrolytes

Poly(ethyl methacrylate) (PEMA)- and poly(2-ethoxyethyl methacrylate) (PEOEMA)-based polymer gel electrolytes with entrapped solutions of lithium perchlorate in propylene carbonate (PC) were prepared by direct, UV-initiated polymerization. The electrolytes were studied using electrochemical methods and they exhibit good ionic conductivity (up to 0.7 mS cm⁻¹ at 20 °C) as well as electrochemical stability up to 2.5 V vs. Cd/Cd²⁺ (5.1 V vs. Li/Li⁺) on gold electrode. The electrolytes have thermal stability up to 125 °C. The electrolytes were successfully tested as ionic conductors in the electrochromic device FTO/WO₃/Li⁺-electrolyte/V₂O₅/FTO using coupled optoelectrochemical methods to discuss the relationship between the electrolyte composition and parameters such as change of transmittance, response time and stability. The transmittance change Δτ was found to be 30-45% at 634 nm.