An aqueous solution sodium ion battery and its positive electrode material, preparation method and application
A sodium ion, aqueous solution technology, applied in the field of materials, can solve problems such as low capacity, and achieve the effects of long cycle life, simple preparation, and stability in air
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Embodiment 1
[0043] Embodiment 1 of the present invention provides a manganese-containing oxide material used for the positive electrode active material of an aqueous solution sodium ion secondary battery, and its general chemical formula is: Na x mn (1-y-z) A y Ti z o2-δ ;
[0044] The A is a doping element, specifically B 3+ 、Al 3+ 、Cr 3+ , Mn 4+ , Fe 3+ , V 3+ 、Mo 6+ One or more of them; the relationship between x, y, z, and δ satisfies: 0≤1-y-z≤x, 0≤z<1-x, and x+3(1-y-z)+ay +4z=2(2-δ); where 0.55≤x≤0.8, -0.02≤δ≤0.02, a is the valence of the doping element A.
[0045] Further, in the above general formula, the value range of x is preferably 0.55≤x≤0.72, and the value range of δ is preferably -0.01≤δ≤0.01.
[0046] Below, with Na 0.66 mn 0.66 Ti 0.34 o 2 The structure of the manganese-containing oxide material will be described in detail by taking an example.
[0047] figure 1 Shown as Na 0.66 mn 0.66 Ti 0.34 o 2 The X-ray diffraction (X-ray diffraction, XRD) pattern...
Embodiment 2
[0052] This embodiment provides a preparation method of a manganese oxide compound material, specifically a solid phase method, such as Figure 4 shown, including:
[0053] Step 401, weighing sodium carbonate, manganese trioxide, the oxide of A and titanium dioxide according to the material ratio of Na:Mn:A:Ti=(1.02~1.05)x:(1-y-z):y:z, Precursor powder is obtained after grinding and mixing;
[0054] The A is a doping element, specifically B 3+ 、Al 3+ 、Cr 3+ , Mn 4+ , Fe 3+ , V 3+ 、Mo 6+ One or more of them; the relationship between x, y, z, and δ satisfies: 0≤1-y-z≤x, 0≤z<1-x, and x+3(1-y-z)+ay +4z=2(2-δ); where 0.55≤x≤0.8, -0.02≤δ≤0.02, a is the valence of the doping element A.
[0055] Preferably, the value range of x is: 0.55≤x≤0.72; the value range of δ is: -0.01≤δ≤0.01.
[0056] Step 402, heat-treating the precursor powder at 650° C.-1000° C. for 8-25 hours to obtain the manganese-containing oxide compound.
[0057] The preferred temperature is 800°C-1000°C, an...
Embodiment 3
[0060] This embodiment provides a method for preparing a manganese oxide-containing material, specifically a sol-gel method, such as Figure 5 shown, including:
[0061] Step 501, weigh sodium acetate, manganese nitrate, salt containing A and tetratitanate according to the ratio of Na:Mn:A:Ti=(1.02~1.05)x:(1-y-z):y:z Butyl esters, respectively dissolved in absolute ethanol, mixed with complexing agent, heated at 50°C-80°C for 5-8 hours to obtain precursor gel;
[0062] The A is a doping element, specifically B 3+ 、Al 3+ 、Cr 3+ , Mn 4+ , Fe 3+ , V 3+ 、Mo 6+ One or more of them; the relationship between x, y, z, and δ satisfies: 0≤1-y-z≤x, 0≤z<1-x, and x+3(1-y-z)+ay +4z=2(2-δ); where 0.55≤x≤0.8, -0.02≤δ≤0.02, a is the valence of the doping element A.
[0063] Preferably, the value range of x is: 0.55≤x≤0.72; the value range of δ is: -0.01≤δ≤0.01.
[0064] In step 502, the precursor gel is pretreated at 250°C-600°C for 2-6 hours, and then heat-treated at 750°C-1000°C fo...
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