Three-dimensional composite metallic lithium negative electrode, metallic lithium battery and apparatus
View Patent ↗A three-dimensional composite metallic lithium negative electrode, a metallic lithium battery, and an apparatus are disclosed. The composite metallic lithium negative electrode includes metallic lithium particles and a three-dimensional polymer framework, where the metallic lithium particles are filled in the three-dimensional polymer framework, and the three-dimensional polymer framework includes lithium-philic fragments, active sites, and polymer-containing moieties. The present application improves a volume effect of the metallic lithium negative electrode in charge and discharge process, which can inhibit side reactions of metallic lithium and electrolyte; increase a specific surface area of the metallic lithium negative electrode, and introduce lithium-philic nano-sites, thereby can guide a uniform deposition of the metallic lithium and effectively inhibit generation of lithium dendrites. In addition, the three-dimensional framework coated with active lithium can effectively reduce risks of brittle SEI film faced by traditional solutions.
1 . A three-dimensional composite metallic lithium negative electrode, comprising:
metallic lithium particles, and
a three-dimensional polymer framework;
wherein the metallic lithium particles are filled in the three-dimensional polymer framework, and the three-dimensional polymer framework comprises lithium-philic fragments, active sites, and polymer-containing moieties, the lithium-philic fragments, the active sites, and the metallic lithium particles are uniformly distributed in the three-dimensional composite metallic lithium negative electrode, a difference in element distribution concentration of the lithium-philic fragments, the active sites, and the metallic lithium particles per square millimeter in a thickness direction of the three-dimensional composite metallic lithium negative electrode is not more than 5%; and
wherein each of the lithium-philic fragments is a fragment of a metal oxide with lithium-philic characteristic, the metal oxide is in a form of particles, and the lithium-philic characteristic refers to be able to reduce a nucleation overpotential of a lithium deposition process, so that the nucleation overpotential of lithium ions in the three-dimensional composite metallic lithium negative electrode is less than 10 mV,
wherein each of the active sites is an active group capable of undergoing a lithiation reaction contained in the three-dimensional polymer framework, and the active group comprises a sulfur-containing group,
wherein the polymer-containing moieties comprise vulcanized and calcinated polyacrylonitrile (SPAN).
2 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein the metal oxide is selected from at least one of magnesium oxide, zinc oxide, copper oxide, lead oxide, bismuth oxide, tin oxide, and silver oxide.
3 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein the active group further comprises a nitrogen-containing group; and,
wherein the polymer-containing moieties further comprise one selected from one of calcinated polyacrylonitrile (PAN), calcinated polyaniline (PANI), vulcanized and calcinated polyaniline (SPANI), calcinated polypyrrole (PPY), and vulcanized and calcinated polypyrrole (SPPY).
4 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a molar ratio of the lithium-philic fragments to the active sites in the three-dimensional polymer framework is 1:5 to 1:60.
5 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a volume average particle diameter of the particles of the metal oxide is 50 nm to 500 nm.
6 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a volume average particle diameter of the metallic lithium particles is 1 μm to 100 μm.
7 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a molar ratio of the lithium-philic fragments to metallic lithium particles is 1:58 to 1:1000.
8 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein the three-dimensional composite metallic lithium negative electrode further comprises a conductive material selected from one or more of carbon nanotubes, conductive carbon black, and graphene.
9 . The three-dimensional composite metallic lithium negative electrode according to claim 8 , wherein an inner diameter of the carbon nanotube is 1 nm˜10 nm, and a length of the carbon nanotube is about 5 μm to 20 μm.
10 . The three-dimensional composite metallic lithium negative electrode according to claim 8 , wherein a content of the conductive material is 5 wt % to 30 wt %.
11 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a weight ratio of the lithium-philic fragments relative to the three-dimensional composite metallic lithium negative electrode is 0.5% to 5%.
12 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a mass ratio of the lithium-philic fragments to the metallic lithium particles is 1:10 to 1:150.
13 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a mass ratio of the three-dimensional polymer framework to the metallic lithium particles is 1:10.
14 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein a pore diameter in the three-dimensional composite metallic lithium negative electrode is 10 μm to 800 μm.
15 . The three-dimensional composite metallic lithium negative electrode according to claim 1 , wherein the sulfur-containing group is selected from at least one of —S—, —S—S—, —S—S—S—, and —S—(S)n—S—, wherein n is an integer.
16 . A metallic lithium battery, comprising a positive electrode, a three-dimensional composite metallic lithium negative electrode, a separator, and an electrolyte, wherein the three-dimensional composite metallic lithium negative electrode comprises:
metallic lithium particles, and
a three-dimensional polymer framework;
wherein the metallic lithium particles are filled in the three-dimensional polymer framework, and the three-dimensional polymer framework comprises lithium-philic fragments, active sites, and polymer-containing moieties, the lithium-philic fragments, the active sites, and the metallic lithium particles are uniformly distributed in the three-dimensional composite metallic lithium negative electrode, a difference in element distribution concentration of the lithium-philic fragments, the active sites, and the metallic lithium particles per square millimeter in a thickness direction of the three-dimensional composite metallic lithium negative electrode is not more than 5%;
wherein each of the lithium-philic fragments is a fragment of a metal oxide with lithium-philic characteristic, the metal oxide is in a form of particles, and the lithium-philic characteristic refers to be able to reduce a nucleation overpotential of a lithium deposition process, so that the nucleation overpotential of lithium ions in the three-dimensional composite metallic lithium negative electrode is less than 10 mV;
wherein the active sites and the metallic lithium particles are uniformly distributed in the three-dimensional composite metallic lithium negative electrode,
wherein each of the active sites is an active group capable of undergoing a lithiation reaction contained in the three-dimensional polymer framework, and the active group comprises a sulfur-containing group,
wherein the polymer-containing moieties comprise vulcanized and calcinated polyacrylonitrile (SPAN).
17 . An apparatus, comprising the metallic lithium battery of claim 16 .