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The LiB compounds in lithium deficient state were prepared by three methods and its crystal structure was investigated by using XRD. It is found that the lattice constant c of the compound will increase step by step with decreasing Li content from 0.2796nm of the normal LiB to 0.2886, 0.2981 and 0.3118nm of the lithium deficient LiB. The change of the lattice constant is reversible.