从废旧电池中回收二水磷酸铁再生LiFePO_(4)/C

使用酸浸—加热回流法从废旧磷酸铁锂电池中回收得到二水磷酸铁,将其作为原料并添加一定量的锂源和碳源,通过高温固相法再生了LiFePO_(4)/C,并研究了温度对再生LiFePO_(4)/C电化学性能的影响。首先采用酸浸—加热回流法对废旧磷酸铁锂正极片进行处理生成FePO_(4)·2H_(2)O,洗涤烘干后研磨得到FePO_(4)·2H_(2)O粉末,XRD表征和ICP测试结果显示回收得到的FePO_(4)·2H_(2)O结构完整、纯度较高。然后在FePO_(4)·2H_(2)O粉末中添加碳源,在高温下制备LiFePO_(4)/C材料,对其进行结构与形貌表征以及电化学测试,发现以葡萄糖为碳源、温度为700℃、葡萄糖量为理论生成磷酸铁锂质量的17%时再生的LiFePO_(4)/C电化学性能最佳,0.3 C倍率下再生的LiFePO_(4)/C首周放电比容量可达141.8 mAh/g,循环100周后容量保持率可维持在94.3%。通过与商用LiFePO_(4)/C进行电化学性能对比,进一步验证了该工艺再生的LiFePO_(4)/C有着优良的电化学性能。

Interface defect induced upgrade of K-storage properties in KFeSO4Fcathode: From lowered Fe-3d orbital energy level to advancedpotassium-ion batteries

KFeSO_(4)F(KFSF)is considered a potential cathode due to the large capacity and low cost.However,the inferior electronic conductivity leads to poor electrochemical performance.Defect engineering can facilitate the electron/ion transfer by tuning electronic structure,thus providing favorable electrochemical performance.Herein,through the regulation of surface defect engineering in reduced graphene oxide(rGO),the Fe–C bonds were formed between KFSF and rGO.The Fe–C bonds formed work in regulating the Fe-3d orbital as well as promoting the migration ability of K ions and increasing the electronic conductivity of KFSF.Thus,the KFSF@rGO delivers a high capacity of 119.6 mAh g^(-1).When matched with a graphite@pitch-derived S-doped carbon anode,the full cell delivers an energy density of 250.5 Wh kg^(-1) and a capacity retention of 81.5%after 400 cycles.This work offers a simple and valid method to develop high-performance cathodes by tuning defect sites.

Regeneration of spent LiFePO4 as a high-performance cathode material by a simultaneous coating and doping strategy

With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal salts are economically inefficient and polluting.Meanwhile,the recycled material obtained by lithium remediation alone has limited performance in cycling stability.Herein,a short method of solid-phase reduction is developed to recover spent LiFePO4 by simultaneously introducing Mg2+ions for hetero-atom doping.Issues of particle agglomeration,carbon layer breakage,lithium loss,and Fe3+defects in spent LiFePO4 are also addressed.Results show that Mg2+addition during regeneration can remarkably enhance the crystal structure stability and improve the Li+diffusion coefficient.The regenerated LiFePO4 exhibits significantly improved electrochemical performance with a specific discharge capacity of 143.2 mAh·g^(−1)at 0.2 C,and its capacity retention is extremely increased from 37.9%to 98.5%over 200 cycles at 1 C.Especially,its discharge capacity can reach 95.5 mAh·g^(−1)at 10 C,which is higher than that of spent LiFePO4(55.9 mAh·g^(−1)).All these results show that the proposed regeneration strategy of simultaneous carbon coating and Mg2+doping is suitable for the efficient treatment of spent LiFePO4.

Lignite-Based Hierarchical Porous C/SiO_(x)Composites as High-Performance Anode for Potassium-Ion Batteries

Silicon oxide(SiO_(x),0<x≤2)has been recognized as a prominent anode material in lithium-ion batteries and sodium-ion batteries due to its high theoretical capacity,suitable electrochemical potential,and earth abundance.However,it is intrinsically poor electronic conductivity and excessive volume expansion during potassiation/depotassiation process hinder its application in potassium-ion batteries.Herein,we reported a hierarchical porous C/SiO_(x)potassium-ion batteries anode using lignite as raw material via a one-step carbonization and activation method.The amorphous C skeleton around SiO_(x)particles can effectively buffer the volume expansion,and improve the ionic/electronic conductivity and structural integrity,achieving outstanding rate capability and cyclability.As expected,the obtained C/SiO_(x)composite delivers a superb specific capacity of 370 mAh g^(-1)at 0.1 A g^(-1)after 100 cycles as well as a highly reversible capacity of 208 mAh g^(-1)after 1200 cycles at 1.0 A g^(-1).Moreover,the potassium ion storage mechanism of C/SiO_(x)electrodes was investigated by ex-situ X-ray diffraction and transmission electron microscopy,revealing the formation of reversible products of K_(6.8)Si_(45.3)and K_(4)SiO_(4),accompanied by generation of irreversible K2O after the first cycle.This work sheds light on designing low-cost Si-based anode materials for high-performance potassium-ion batteries and beyond.

KVPO_(4)F/carbon nanocomposite with highly accessible active sites and robust chemical bonds for advanced potassium-ion batteries

KVPO_(4)F(KVPF)has been extensively investigated as the potential cathode material for potassium-ion batteries(PIBs)owing to its high theoretical capacity,superior operating voltage,and three-dimensional Kt conduction pathway.Nevertheless,the electrochemical behavior of KVPF is limited by the inherent poor electronic conductivity of the phosphate framework and unstable electrode/electrolyte interface.To address the above issues,this work proposes an infiltration-calcination method to confine the in-situ grown KVPF into the mesoporous carbon CMK-3(denoted KVPF@CMK-3).The assembled KVPF@CMK-3 nanocomposite features three-dimensional interconnected carbon channels,which not only offer abundant active sites and significantly accelerate K t/electron transport,but also prevent the growth of KVPF nanoparticle agglomerates,hence stabilizing the structure of the material.Additionally,V–F–C bonds are created at the interface of KVPF and CMK-3,which reduce the loss of F and stabilize the electrode interface.Thus,when tested as a cathode material for PIBs,the KVPF@CMK-3 nanocomposite delivers superior reversible capacitiy(103.2 mAh g^(-1) at 0.2 C),outstanding rate performance(90.1 mAh g^(-1) at 20 C),and steady cycling performance(92.2 mAh g^(-1) at 10 C and with the retention of 88.2%after 500 cycles).Moreover,its potassium storage mechanism is further examined by ex-situ XRD and ex-situ XPS techniques.The above synthetic strategy demonstrates the potential of KVPF@CMK-3 to be applied as the cathode for PIBs.

检测磷酸铁锂电池热失控气体C_(2)H_(4)的MoS_(2)@c-MOF传感器研究

磷酸铁锂电池由于其固有的放热特性以及在电解液中使用易燃有机溶剂,存在着巨大的热失控风险,可能引发严重的火灾事故,因此对磷酸铁锂电池热失控气体的实时监测已成为当前研究的重点。针对目前SnS_(2)/MoS_(2)气体传感器存在工作温度高、灵敏度低等难题,基于导电金属有机框架c-MOF在提升导电性能和增强选择性方面的独特优势,开展了SnS_(2)/MoS_(2)@c-MOF气敏材料制备、C_(2)H_(4)传感特性及检测机理研究。首先利用水热法成功制备了SnS_(2)@c-MOF和MoS_(2)@c-MOF复合气敏材料,并利用XRD和SEM表征手段验证了复合气敏材料的成功制备。然后,制成了平面式SnS_(2)@c-MOF和MoS_(2)@c-MOF传感器,测试了传感器对C_(2)H_(4)的浓度响应、响应恢复时间和稳定性。结果表明,MoS_(2)@c-MOF传感器对10ppm C_(2)H_(4)气体的响应值为4.42%,响应时间/恢复时间为121 s/124 s,优于SnS_(2)@c-MOF传感器,同时具有较好的长期稳定性。最后,基于密度泛函理论,从吸附能、吸附距离、态密度和电荷转移角度对比分析了SnS_(2)@c-MOF和MoS_(2)@c-MOF材料对C_(2)H_(4)的吸附性能和响应特性。本文研究成果为开发用于检测磷酸铁锂电池热失控产生的C_(2)H_(4)气体的高性能MoS_(2)@c-MOF传感器奠定了基础。

Synthesis of porous nano/micro structured LiFePO_4/C cathode materials for lithium-ion batteries by spray-drying method

In order to enhance electrochemical properties of LiFePO4 （LFP） cathode materials, spherical porous nano/micro structured LFP/C cathode materials were synthesized by spray drying, followed by calcination. The results show that the spherical precursors with the sizes of 0.5-5 μm can be completely converted to LFP/C when the calcination temperature is higher than 500 ℃. The LFP/C microspheres obtained at calcination temperature of 700 ℃ are composed of numerous particles with sizes of -20 nm, and have well-developed interconnected pore structure and large specific surface area of 28.77 mE/g. The specific discharge capacities of the LFP/C obtained at 700 ℃ are 162.43, 154.35 and 144.03 mA.h/g at 0.5C, 1C and 2C, respectively. Meanwhile, the capacity retentions can reach up to 100% after 50 cycles. The improved electrochemical properties of the materials are ascribed to a small Li＋ diffusion resistance and special structure of LFP/C microspheres.

Synthesis and electrochemical performances of spherical LiFePO_4 cathode materials for Li-ion batteries

Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g-1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g-1. The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.

Electrochemical performance of carbon nanotube-modified LiFePO_4 cathodes for Li-ion batteries

Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and electrochemical performances of as-prepared LiFePO4 were evaluated by means of transmission electron microscopy (TEM), charge-discharge test, electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV). CNTs contribute to the interconnection of the isolated LiFePO4 or carbon particles. For the CNTs-modified LiFePO4, it exhibits excellent performance in terms of both specific capacity and cycle life. The initial discharge capacity is 147.9 mA·h/g at 0.2C rate and 134.2 mA·h/g at 1C rate, keeping a capacity retention ratio of 97% after 50 cycles. The results from EIS indicate that the impedance value of the solid electrolyte interface decreases. The cyclic voltammetric peak profiles is more symmetric and spiculate and there are fewer peaks. CNTs are promising conductive additives candidate for high-power Li-ion batteries.

The Surface Coating of Commercial LiFePO_4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

The requirement of energy-storage equipment needs to develop the lithium ion battery(LIB) with high electrochemical performance. The surface modification of commercial LiFePO_4(LFP) by utilizing zeolitic imidazolate frameworks-8(ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances.In this work, the carbonized ZIF-8(C_(ZIF-8)) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/C_(ZIF-8) sample. The N_2 adsorption and desorptionisotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/C_(ZIF-8) cathode-active material delivers a discharge specific capacity of 159.3 m Ah g^(-1) at 0.1 C and a discharge specific energy of 141.7 m Wh g^(-1) after 200 cycles at 5.0 C(the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity,the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/C_(ZIF-8) cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.

A novel synthetic route for LiFePO_4/C cathode materials by addition of starch for lithium-ion batteries

LiFePO4/Carbon composite cathode material was prepared using starch as carbon source by spray-pelleting and subsequent pyrolysis in N2. The samples were characterized by XRD, SEM, Raman, and their electrochemical performance was investigated in terms of cycling behavior. There has a special micro-morphology via the process, which is favorable to electrochemical properties. The discharge capacity of the LiFePO4.C composite was 170 mAh g-1, equal to the theoretical specific capacity at 0.1 C rate. At 4 C current density, the specific capacity was about 80 mAh g-1, which can satisfy for transportation applications if having a more flat discharge flat.

Influence of Ti^(4+) doping on electrochemical properties of LiFePO_4/C cathode material for lithium-ion batteries

To improve the performance of LiFePO4, single phase Li1-4xTixFePO4/C (x=0, 0.005, 0.010, 0.015) cathodes were synthesized by solid-state method. A certain content of glucose was used as carbon precursor and content of carbon in every final product was about 3.5%. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy observations(SEM), charge/discharge test, carbon analysis and electrochemical impedance spectroscopy(EIS). The results indicate that the prepared samples have ordered olivine structure and doping of the low concentration Ti^(4+) does not affect the structure of the samples. The electrochemical capabilities evaluated by charge-discharge test show that the sample with 1% Ti^(4+) (molar fraction) has good electrochemical performance delivering about an initial specific capacity of 146.7 mA·h/g at 0.3C rate. Electrochemical impedance spectroscopy measurement results show that the charge transfer resistance of the sample could be decreased greatly by doping an appropriate amount Ti^(4+).

Controllable synthesis of high loading LiFePO_4/C nanocomposites using bimodal mesoporous carbon as support for high power Li-ion battery cathodes

Mesoporous LiFePO4/C composites containing 80 wt% of highly dispersed LiFePO4 nanoparticles(4-6 nm) were fabricated using bimodal mesoporous carbon(BMC) as continuous conductive networks. The unique pore structure of BMC not only promises good particle connectivity for LiFePO4, but also acts as a rigid nano-confinement support that controls the particle size. Furthermore, the capacities were investigated respectively based on the weight of LiFePO4 and the whole composite. When calculated based on the weight of the whole composite, it is 120 mAh·g-1at 0.1 C of the high loading electrode and 42 mAh·g-1at 10 C of the low loading electrode. The electrochemical performance shows that high LiFePO4 loading benefits large tap density and contributes to the energy storage at low rates, while the electrode with low content of LiFePO4 displays superior high rate performance, which can mainly be due to the small particle size, good dispersion and high utilization of the active material, thus leading to a fast ion and electron diffusion.

Physical and Electrochemical Properties of Doped LiFePO4 as Cathode Material for Lithium-Ion Batteries

LiFePO4 cathode material was synthesized by a solid-state reaction using doping several elements (Nb5 + ,Zr4 + ). The starting materials were mixed with a high-efficient sander and treated thermally under flowing N2. The samples were characterized by X-ray diffraction (XRD), field-emission gun electron microscopy (FEG), and their electrochemical performance was investigated in the term of cycling behavior. Room temperature discharge capacity about 140.6 mA·h·g-1 was obtained at C/5 rate.

Experimental study on thermal characteristics of LiFePO_4 power batteries

As an important high-energy chemical power source, lithium-ion power batteries come up to application problems of thermal performance, such as extended temperature range and high power charge ＆ discharge. LiFeP04 battery is applied and developed well recently, its charge and discharge experiment at different temperatures and hybrid pulse power characterization （HPPC） test are analyzed, and the optimal temperature range of LiFeP04 battery is put forward. In order to provide experimental suggestion of power battery application and its thermal management, internal resistance, influencing factor of electromotive force and entropy change state of charge （SOC）, battery thermal characteristic of different charge ＆ discharge rates are summarized.

Preparation of LiFePO_4 for lithium ion battery using Fe_2P_2O_7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.

An Electro-thermal Model and Its Application on SOE Estimation for LiFePO_(4)/C Battery

The state of energy(SOE)is an important state parameter and evaluation index to indicate the residual energy for LiFeP0_(4)/C battery.In order to improve the estimation accuracy of SOE,the influence of the thermal energy inside the battery is researched by the electro-thermal energy model and an enhanced algorithm considering electrical energy and thermal energy is proposed to realize the accurate estimation of SOE.The novel estimation model is verified by lots of experiments that it's highly similar to the situation of actual energy consumption and has a high accuracy of SOE estimation.

Electrochemical performance of LiFePO_4 cathode material for Li-ion battery

In the search for improved materials for rechargeable lithium batteries, LiFePO4 offers interesting possibilities because of its low raw materials cost, environmental friendliness and safety. The main drawback with using the material is its poor electronic conductivity and this limitation has to be overcome. Here Al-doped LiFePO4/C composite cathode materials were prepared by a polymer-network synthesis technique. Testing of X-ray diffraction, charge-discharge, and cyclic voltammetry were carried out for its performance. Results show that Al-doped LiFePO4/C composite cathode materials have a high initial capacity, good cycle stability and excellent low temperature performance. The electrical conductivity of LiFePO4 material can be obviously improved by doping Al. The better electrochemical performances of Al-doped LiFePO4/C composite cathode materials have a connection with its conductivity.

A Novel Real-Time State-of-Health and State-of-Charge Co-Estimation Method for LiFePO_4 Battery

The state of charge （SOC） and state of health （SOH） are two of the most important parameters of Li-ion batteries in industrial production and in practical applications. The real-time estimation for these two parameters is crucial to realize a safe and reliable battery application. However, this is a great problem for LiFePO4 batteries due to the large constant potential plateau in the charge/discharge process. Here we propose a combined SOC and SOH co-estimation method based on the experimental test under the simulating electric vehicle working condition. A first-order resistance-capacitance equivalent circuit is used to model the battery cell, and three parameter values, ohmic resistance （Rs）, parallel resistance （Rp） and parallel capacity （Cp）, are identified from a real-time experimental test. Finally we find that Rp and Cp could be utilized to make a judgement on the SOIl. More importantly, the linear relationship between Cp and the SOC is established to make the estimation of the SOC for the first time.

Studies on Electrochemical Property of LiFePO_4/C as Cathode Material for Lithium Ion Batteries

LiFePO4/C samples were prepared at different temperatures by adding sngar to the synthetic precursor. The samples were characterized by X-ray diffraction（XRD）. Their crystal phases show an olivine structure. Only the sample obtained at 700℃ has a larger discharge capacity, which has good electrochemical properties： its discharge specific capacity is 120. 3 mAh/g at a current of 0. 05 mA, and its capacity fade is very low after 20 cycles. It is demonstrated that the best synthetic temperature should be 700℃.