• Transactions on Electrical and Electronic Materials
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• 제15권6호
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• pp.320-323
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• 2014

Ga-doped $LiFePO_4$ cathode materials were synthesized using a hydrothermal method. The microstructural characteristics and electrochemical performances were systematically investigated using field emission scanning electron microscopy, high-resolution X-ray diffraction, energy dispersive X-ray spectroscopy, charge-discharge cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. Among the as-prepared samples, $LiFe_{0.96}Ga_{0.04}PO_4$ demonstrates the best electrochemical properties in terms of discharge capacity, electrochemical reversibility, and cycling performance with an initial discharge capacity of $125mAh\;g^{-1}$ and high lithium ion diffusion coefficient of $1.38{\times}10^{-14}cm^2s^{-1}$ (whereas for $LiFePO_4$, these were $113mAh\;g^{-1}$ and $8.09{\times}10^{-15}cm^2\;s^{-1}$, respectively). The improved electrochemical performance can be attributed to the facilitation of Li+ ion effective diffusion induced by $Ga^{3+}$ substitution.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.852-856
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• 2011

The lithium ion diffusion coefficients of bare, carbon-coated and Cr-doped $LiFePO_4$ were obtained by fitting the discharge curves of each half cell with Li metal anode. Diffusion losses at discharge curves were acquired with experiment data and fitted to equations. Theoretically fitted equations showed good agreement with experimental results. Moreover, theoretical equations are able to predict lithium diffusion coefficient and discharge curves at various discharge rates. The obtained diffusion coefficients were similar to the true diffusion coefficient of phase transformation electrodes. Lithium ion diffusion is one of main factors that determine voltage drop in a half cell with $LiFePO_4$ cathode and Li metal anode. The high diffusion coefficient of carbon-coated and Cr-doped $LiFePO_4$ resulted in better performance at the discharge process. The performance at high discharge rate was improved much as diffusion coefficient increased.

• 한국재료학회지
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• 제21권11호
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• pp.587-591
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• 2011

The effect of the precipitator (NaOH, $NH_4OH$) and the amount of the precipitator (150, 200, 250, 300 ml) on the formation of $Fe_3(PO_4)_2$, which is the precursor used for cathode material $LiFePO_4$ in Li-ion rechargeable batteries was investigated by the co-precipitation method. A pure precursor of olivine $LiFePO_4$ was successfully prepared with coprecipitation from an aqueous solution containing trivalent iron ions. The acid solution was prepared by mixing 150 ml $FeSO_4$(1M) and 100 ml $H_3PO_4$(1M). The concentration of the NaOH and $NH_4OH$ solution was 1 M. The reaction temperature (25$^{\circ}C$) and reaction time (30 min) were fixed. Nitrogen gas (500 ml/min) was flowed during the reaction to prevent oxidation of $Fe^{2+}$. Single phase $Fe_3(PO_4)_2$ was formed when 150, 200, 250 and 300 ml NaOH solutions were added and 150, 200 ml $NH_4OH$ solutions were added. However, $Fe_3(PO_4)_2$ and $NH_4FePO_4$ were formed when 250 and 300 ml $NH_4OH$ was added. The morphology of the $Fe_3(PO_4)_2$ changed according to the pH. Plate-like lenticular shaped $Fe_3(PO_4)_2$ formed in the acidic solution below pH 5 and plate-like rhombus shaped $Fe_3(PO_4)_2$ formed around pH 9. For the $NH_4OH$, the pH value after 30 min reaction was higher with the same amount of additions of NaOH and $NH_4OH$. It is believed that the formation mechanism of $Fe_3(PO_4)_2$ is quite different between NaOH and $NH_4OH$. 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.

• Journal of Electrochemical Science and Technology
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• 제3권3호
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• pp.135-142
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• 2012

Over the past few years, $LiFePO_4$ has been actively studied as a cathode material for lithium-ion batteries because of its advantageous properties such as high theoretical capacity, good cycle life, and high thermal stability. However, it does not have a very good power capability owing to the low lithium-ion diffusivity and poor electronic conductivity. Reduction in particle size of $LiFePO_4$ to the scale of nanometers has been found to dramatically enhance the above properties, according to many earlier reports. However, because of the intrinsically low tap density of nanomaterials, it is difficult to commercialize this method. Many studies are being carried out to improve the volumetric energy density of this material and many methods have been reported so far. This paper provides a brief summary of the synthesis methods and electrochemical performances of micro-spherical $LiFePO_4$ having high volumetric energy density.

• 한국재료학회:학술대회논문집
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• 한국재료학회 1996년도 재료학회 추계학술발표회
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• pp.98-98
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• 1996

• 한국광물학회지
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• 제22권1호
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• pp.63-72
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• 2009

개량된 MA법으로 합성된 $LiFe(PO_4)/C$에 대해 X-선 회절분석을 실시하여 리트벨트법에 의해 결정학적 연구를 수행하였다. 리트벨트 계산 결과 리트벨트 R 지수 값은 $R_p=8.14%,\;R_{wp}=11.1%,\;R_{exp}=9.09%,\;R_B=3.88%$, S (GofF, Goodness of fit) = 1.2으로 계산이 잘 이루어졌음을 알 수 있다. $LiFePO_4/C$는 공간군 Pnma를 가지며, 격자상수 값은 a = 10.3229(3)${\AA}$, b = 6.0052(2) ${\AA}$, c = 4.6939(1) ${\AA}$이고 체적값은 V = 290.98(1) ${\AA}^3$으로 기존 다른 합성법의 연구결과와 잘 일치한다. 분말 입자는 고순도를 가지고 나노 크기($65{\sim}90nm$)로 기존 MA법보다 상대적으로 미세하고 균질도가 향상되었다. 따라서 개량된 MA법은 상업용 리튬 2차 전지의 양극물질 생산을 위한 우수한 제조법으로 판단된다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2007년도 추계학술대회 논문집
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• pp.316-316
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• 2007

리튬폴리머 전지용 정극활물질인 $LiFePO_4$를 수열법으로 합성하였다. 제조한 정극활물질 $LiFePO_4$는 X-ray 회절분석을 통하여 olivine 구조임을 확인하였다. 전극 제조 시 첨가된 도전재의 종류에 따른 전기화학적 특성변화를 알기 위하여, Acetylene Black, Super-Black, Multi-Walled Carbon Nanotube(MWCNT), SP270을 도전재로 제조된 정극활물질과 PVDF를 결합제로 사용하였다. 셀은 제조된 정극과 고체전해질 $25PVDFLiCIO_4EC_{10}PC_{10}$를 사용하고, 부극은 금속리튬으로 coin 타입의 cell을 조립하여 충방전을 진행하였다. 충방전 진행결과, Multi-Walled Carbon Nanotube(MWCNT)를 도전재로 사용하였을 경우, 초기 방전용량은 94mAh/g, 100cycle 후에는 약 93mAh/g인 기타 도전재를 사용하였을 때보다 안정하고 높은 방전용량을 나타내었다. 이때의 충방전 전류밀도는 0.1mAh/g이고 전압범위 는 2.5~4.3V이었다.

• Bulletin of the Korean Chemical Society
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• 제29권9호
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• pp.1737-1741
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• 2008

The electrochemical and thermal stability of $LiNi_{0.8}Co_{0.16}Al_{0.04}O_2$ were studied before and after $Co_3(PO_4)_2$ coating. Different to conventional coating material such as $ZrO_2$ or AlPO4, the coating layer was not detected clearly by TEM analysis, indicating that the $Co_3(PO_4)_2$ nanoparticles effectively reacted with surface impurities such as $Li_2CO_3$. The coated sample showed similar capacity at a low C rate condition. However, the rate capability was significantly improved by the coating effect. It is associated with a decrease of impedance after coating because impedance can act as a major barrier for overall cell performances in high C rate cycling. In the DSC profile of the charged sample, exothermic peaks were shifted to high temperatures and heat generation was reduced after coating, indicating the thermal reaction between electrode and electrolyte was sucessfully suppressed by $Co_3(PO_4)_2$ nanoparticle coating.

• 한국세라믹학회:학술대회논문집
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• 한국세라믹학회 2003년도 추계총회 및 연구발표회 초록집
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• pp.200.2-200
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• 2003

• Journal of Electrochemical Science and Technology
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• 제4권3호
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• pp.113-118
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• 2013

Fluorophosphate, $Na_2MnPO_4F$ as new cathode material was synthesized by carbothermal treatment method. Prepared $Na_2MnPO_4F$ has particle size under 100 nm and residual carbon exists in surface of $Na_2MnPO_4F$. Additional carbon coating was performed in order to increase the electrochemical properties. Even capacity and overpotential were improved by carbon coating using mechanical ball milling, the reduced crystallinity limited the drastic improvement of the electrochemical properties. To solve this problem, re-heat treatment was involved to recover crystallinity and then notable improvement of electrochemical properties was obtained. Specific amount of $Li^+$ that participates in electrochemical $Li^+$ insertion / extraction reaction, was x = 1 in $Li_xNa_{2-x}MnPO_4F$ within the voltage range of 2.0 to 4.8 V. The doubled capacity by 2 electron reaction can be obtained when NMPF is charged to higher voltage over 4.8 V.