Liquid phase exfoliation of natural graphite is an industrially effective solution for graphene preparation. However, many countries have identified natural graphite as a strategic resource and restricted its mining. In this report, we used abundant and readily available needle coke (NC) as a graphene exfoliation precursor and sodium carboxymethyl cellulose (CMC) as a dispersant to prepare a sandwich structured conductive graphitized NC nanosheets (GNCNs) by liquid phase exfoliation, freeze-drying and high-temperature graphitization, in which a graphene layer is sandwiched between two thin CMC layers. CMC could increase the liquid absorption and retention ability of the conductive agent and improve the migration rate of lithium ions. The highly ordered graphene layer could accelerate the transmission of electrons. The GNCNs with 0.4 wt% CMC addition showed good rate performance (144.6 mAh g− 1 at 5 C) and high cycle stability (96.2% after 200 cycles at 1 C) for LiFePO4 (LFP) battery. The traditional Super-P (SP) conductive agent exhibited low-rate performance (113.9 mAh g− 1 at 5 C) and cycle performance (89.9% after 200 cycles at 1 C). This study offers a novel approach to selecting graphene precursors and has promising applications for conductive additives in high-performance LFP batteries.

The effect of the precipitator (NaOH, NH4OH) and the amount of the precipitator (150, 200, 250, 300 ml) on the formation of Fe3(PO4)2, which is the precursor used for cathode material LiFePO4 in Li-ion rechargeable batteries was investigated by the co-precipitation method. A pure precursor of olivine LiFePO4 was successfully prepared with coprecipitation from an aqueous solution containing trivalent iron ions. The acid solution was prepared by mixing 150 ml FeSO4(1M) and 100 ml H3PO4(1M). The concentration of the NaOH and NH4OH solution was 1 M. The reaction temperature (25˚C) and reaction time (30 min) were fixed. Nitrogen gas (500 ml/min) was flowed during the reaction to prevent oxidation of Fe2+. Single phase Fe3(PO4)2 was formed when 150, 200, 250 and 300 ml NaOH solutions were added and 150, 200 ml NH4OH solutions were added. However, Fe3(PO4)2 and NH4FePO4 were formed when 250 and 300 ml NH4OH was added. The morphology of the Fe3(PO4)2 changed according to the pH. Plate-like lenticular shaped Fe3(PO4)2 formed in the acidic solution below pH 5 and plate-like rhombus shaped Fe3(PO4)2 formed around pH 9. For the NH4OH, the pH value after 30 min reaction was higher with the same amount of additions of NaOH and NH4OH. It is believed that the formation mechanism of Fe3(PO4)2 is quite different between NaOH and NH4OH. Further investigation on this mechanism is needed. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and the pH value was measured by pH-Meter.

유사 올리빈 구조를 가지는 탄소코팅 합성 Li+Fe2+(PO4)3- 분말시료에 대한 상온-고압실험을 대칭 다이아몬드 앤빌기기를 이용하여 35.0 GPa까지 시행하였다. LiFePO4의 압축 데이터를 이용하여 계산된 체적탄성률은 130.1±10.3 GPa이다. 18 GPa 이상의 압력에서 d = 3.386 a 위치에 새로운 피크가 관찰되고 35 GPa에서는 d = 2.854 a에 또 다른 피크가 관찰되고 있으나 주 결정구조는 사방정계인 것으로 판단된다. 압력에 대한 단위 포 부피의 압축은 M1(Li+O6)의 수축이 두드러지고 M2(Fe2+O6)와 사면체(PO4)의 수축은 상대적으로 작은 것으로 나타났다.

개량된 MA법으로 합성된 LiFe(PO4)/C에 대해 X-선 회절분석을 실시하여 리트벨트법에 의해 결정학적 연구를 수행하였다. 리트벨트 계산 결과 리트벨트 R 지수 값은 Rp=8.14%, Rwp=11.1%, Rexp=9.09%, RB=3.88%, S (GofF, Goodness of fit) = 1.2으로 계산이 잘 이루어졌음을 알 수 있다. LiFePO4/C는 공간군 Pnma를 가지며, 격자상수 값은 a = 10.3229(3)a, b = 6.0052(2) a, c = 4.6939(1) a이고 체적값은 V = 290.98(1) a3으로 기존 다른 합성법의 연구결과와 잘 일치한다. 분말 입자는 고순도를 가지고 나노 크기(65~90nm)로 기존 MA법보다 상대적으로 미세하고 균질도가 향상되었다. 따라서 개량된 MA법은 상업용 리튬 2차 전지의 양극물질 생산을 위한 우수한 제조법으로 판단된다.